Polyphosphinites and a process for their preparation

ABSTRACT

Compounds of the formula ##STR1## WHEREIN Z is alkyl with 2 to 6 carbon atoms, x is oxygen, NH or sulfur, n and m are integers from 2 to 6, r is zero or 1, R 4 , R 5  R 6  and R 7  are hydrogen or methyl and R 3  is methyl, ethyl or phenyl. They are obtained by reacting 1 mole of a compound of formula 
     
         Z--(X--H).sub.n 
    
     with n.m moles of an alkyleneoxide or alkylenecarbonate of the formulas ##STR2## and n(m+r) moles of a phospholane of formula ##STR3## These compounds are used as flameproofing agents especially for pile carpets.

The present invention relates to a process for the preparation ofpolyaddition products containing phosphorus.

In contrast to polycondensation processes, polyaddition reactions do notform any waste products which need to be separated and, if necessary, bedestroyed or -- in the case of recycling -- be purified.

Thus, it is possible in a particularly easy manner to introducehomogeneous atom groupings into basis molecules by way of polyadditionreactions. In this way, for example, polyethers carrying hydroxylterminal groups having specific properties can be prepared in a singlevery easy reaction step by polyaddition of alkylene oxides to compoundswith active hydrogen atoms.

The synthesis of easily accessible polyaddition products havingrecurrent atom groups containing phosphorus, especially phosphinic acidester groups, has not been known so far. However, easily accessiblesubstances having a high phosphorus content are of particular interestdue to the valuable specific properties of phosphorus functions.

The addition of 2,5-di-oxo-1,2-oxa-phospholanes to monovalent alcoholsand monovalent amines with the formation of phosphinic acids has alreadybeen described. The addition of 1,2-alkylene oxides todialkyl-phosphinic acids is also already known. In these cases,compounds having only one phosphorus atom per molecule are obtained.

The present invention provides compounds having the general formula##STR4## in which

X stands for identical or different radicals selected from the group ofO, S and/or NR¹ with R¹ being hydrogen or (C₁ -C₄)-alkyl, preferablyhydrogen or methyl,

R³ is a (C₁ -C₄)-alkyl group which may be substituted, preferablymonosubstituted, by halogen, especially chlorine, a cycloalkyl grouphaving up to 8 carbon atoms, especially cyclopentyl, cyclohexyl, analkenyl group having up to 4 carbon atoms, especially vinyl and allyl, aphenyl or benzyl group optionally substituted by halogen, preferablychlorine and/or bromine, and preferably carrying 1 to 3 substituents,

R⁴ is hydrogen or a (C₁ -C₄)-alkyl group, preferably methyl,

R⁵ is hydrogen or a (C₁ -C₂)-alkyl group, preferably methyl, with atleast one of the radicals R⁴ and R⁵ preferably being hydrogen,

R⁶ is hydrogen, methyl, chloromethyl,

R⁷ is hydrogen, methyl or ethyl, preferably hydrogen,

m stands for numbers in the range of from 1 to 20, preferably from 2 to20, especially from 2 to 6,

n stands for numbers in the range of from 1 to 6, preferably from 2 to6,

r is 0 or 1, preferably 0,

Z is a n-valent radical of the group consisting of: straight-chain orbranched hydrocarbon radicals having from 1 to 18, preferably from 1 to12, carbon atoms which may be interrupted by up to 8 -O-atoms, generallyup to (q/2-1) --O-atoms, if q is the number of carbon atoms in Z, and/orby up to 3 --S-atoms and/or NR² radicals with R² being (C₁ -C₄)-alkyl,especially methyl, and/or may be substituted by fluorine, chlorine,bromine atoms, preferably Cl and Br, while carrying preferablysubstituents in a number of up to half the H-atoms contained in Z,especially from 1 to 4; cyclohexyl radicals which may be substituted byfrom 1 to 3, preferably one straight-chain or branched and/orunsaturated alkyl radical having from 1 to 4 carbon atoms, or by a (C₁-C₄)-alkyl radical carrying preferably up to 4 F, Cl, or Br-atoms,aromatic or araliphatic radicals which are derived from benzene, alkylbenzenes having up to 18 carbon atoms, from naphthalene, diphenyl,diphenylmethane, diphenylethane, or 2,2-diphenylpropane, and which maybe substituted in the nucleus by 1 or 2 methoxy and/or ethoxy groups,and which may be substituted in the nucleus and/or the lateral chains byF, Cl or Br-atoms, preferably carrying up to 5 substituents, orphosphate-containing radicals of the general formula ##STR5## in which

n₁, n₂ are independently from each other 0 and 1 and

R⁹ stands for alkyl, hydroxyalkyl, optionally (C₁ -C₂)-alkylated and/or-dialkylated aminoalkyl, halogeno- (preferably chloro-)alkyl having 1 to3 carbon atoms, alkenyl having 2 or 3 carbon atoms or phenyl optionallysubstituted by 1 or 2 halogen atoms, preferably Cl, or Br,

R¹⁰, R¹¹ may be defined as R⁹ - if the pertinent n₁ and/or n₂ equals 0-- with the restriction that for n₁ = n₂ = 0 at least one of theradicals R¹⁰, R¹¹ is an (C₁ --C₃)-- alkylene radical or, if thepertinent n₁ and/or n₂ equals 1, is a straight-chain or branchedalkylene radical having from 2 to 5 carbon atoms or is the radical##STR6## or represent phosphorus-containing radicals of the generalformula ##STR7## with n₁, R¹⁶, R¹¹ being defined as in Z₁ and R₁₂ beinga straight-chain or branched (C₁ -C₆)-alkylene, phenylene, xylyleneradical or a radical ##STR8## with Y = OH, NH₂ and R¹³ = (C₁ -C₃)-alkyl,or phosphorus-containing radicals of the general formula ##STR9## inwhich R⁴, R⁵, R⁶, R⁷ are defined as in formula I above

and R¹⁴ is defined as R³ or represents the group --O--CHR⁶ --CHR⁷ --.

Preference is given in particular to compounds of the formula I in whichZ is alkyl having 2 to 6 carbon atoms, X is oxygen, n and m are numbersof from 2 to 6, r is 0 and R⁴ to R⁷ is hydrogen or methyl and R³ ismethyl, ethyl or phenyl.

The invention further provides mixtures of compounds of the formula I.

Moreover, the invention provides a process for the preparation of thecompounds of formula I, which comprises mixing a compound of the formula

    Z(--X--H).sub.n                                            (II)

(a₁) with the about n times molar amount of a phospholane of the formula##STR10## heating it at a temperature of from 0° to 180° C, preferably80° to 150° C, to give a phosphinic acid of the formula ##STR11## and,when this reaction has been completed, which can be seen from thedisappearing of the phospholane peak at 5 500 mμ,

(a₂) reacting the product thus obtained with the about n times molaramount of an alkylene oxide of the formula ##STR12## or of an alkylenecarbonate of the formula ##STR13## to give a phosphinicacid-(hydroxyalkyl)-ester of the formula ##STR14## and, when thisreaction has been completed, which can be seen from the acid numberbeing 0, repeating the operation a₁ (m-1+r) times and following everyoperation a₁ repeating operation a₂ -- (m-1) times altogether -- or,preferably,

(b) mixing a compound of the formula II with the n.m times molar amountof an alkylene oxide of the formula IV or of an alkylene carbonate ofthe formula V and with the about n(m+r) times molar amount of aphospholane of the formula III at a temperature of from 10° to 180° C,preferably 20° to 120° C, and maintaining the mixture after the reactionheat has disappeared, preferably while stirring, at the reactiontemperature indicated below, until the reaction has been completed,which can be seen from the disappearing of the phospholane peak or ofthe carbon dioxide development and/or for r = O, also of the acidnumber.

In formulae II through V the symbols are defined as in formula I.

The reaction of the phosphinic acids of the formula IIa with thealkylene oxides of the formula IV is carried out at a temperature offrom 80° to 180° C, preferably from 100° to 150° C. If alkylenecarbonates of the formula V are used, the reaction temperature is in therange of from 130° to 250° C, preferably from 160° to 220° C.

The process of the invention is generally carried out by introducing thecompound of the formula III and adding compound II at a temperatureexceeding its melting point, preferably at reaction temperature. Theprocess may also be effected vice versa, however. After the reactionheat has cooled off, the alkylene oxide IV is added in the gaseous orliquid phase, depending on its boiling point. In order to prevent lossesof volatile substances, it is advantageous to work while using a refluxcondenser and/or to carry out the process in a closed vessel underautogenous pressure, which is essentially determined by the steampressure of the alkylene oxides. However, the alkylene oxides may alsobe used in any desired excess amount, preferably in an amount exceedingthe necessary quantity 1.2 to 2 times, and the alkylene oxide escapingthe reaction mixture may be recovered in known manner, for example bycondensation. The reaction with alkylene carbonates of the formula V maybe effected in a way that the compounds of formulae V and III areintroduced at room temperature and compound II is slowly added at atemperature above solution temperature. However, if compound II is notan amine, it may be introduced simultaneously. The reaction temperaturesdeveloping in the reaction of compounds II and III remain harmless inthe presence of the alkylene carbonates V.

By adding basic catalysts in an amount of from 0.05 to 4.0%, preferably0.2 to 2.0%, calculated on the sum of the compounds III and IV used,which are selected preferably from the group of alkali metal hydroxides,such as NaOH, KOH, alkali metal-(C₁ -C₄)-alcoholates, such asNa-methylate, K-tert.-butylate, alkali metal-(bi)-carbonates, such assodium carbonate, potassium carbonate, Na-, K-bicarbonate, the reactionrates are markedly increased. Depending on the reaction temperature, thereaction time is generally in the range of from about 1 to 120 hours,preferably from 1 to 20 hours. Naturally, it becomes longer with theincrease of m, in particular for m>4, than for a lower m.

Naturally, it is also possible to produce basis compounds of formula IIin situ by reacting alkylene oxides and/or alkylene carbonates with freecarboxylic, phosphinic or phosphonic acids and to further react the sameaccording to the invention. In this case, an additional s-molar amountof alkylene oxides or alkylene carbonates would be required, if s is thenumber of the free acid groups.

This formation of the compounds of the invention having recurrent atomgroupings, starting from a bivalent alcohol, such as glycol (with --X--being --O--, Z = C₂ H₄ and n being 2) as basis compound and using, forexample, alkylene carbonate, may be described by the following scheme:##STR15##

With further molecules of III and IV and/or V, the chain can still grow.When m is the number of molecules V used per growing chain, acids 1, 2,3, 4 etc. (generally m+r) are always formed, if one more mole of III(r=1) rather than of IV and/or V (generally m+1 moles III) is used.

Neutral 2-hydroxyalkylesters 1, 2, 3, 4 etc. are formed, if the numberof the reacted molecules IV and/or V is at least equal to the number ofthe molecules of II, i.e. if it is also at least equal to m (r= O).Analogous formulations are obtained, if instead of a bivalent alcohol,for example glycol (n=2) n-valent alcohols of the general formulaZ(--OH)_(n) are used as starting products, with Z having the generalmeaning indicated above. In case there are not present alcohols as basismolecules, but for example any amines or mercapto compounds, the "acids1, 2, 3, 4 etc." and "esters 1, 2, 3, 4 etc." being formed differ fromthose formulated with glycol as a basis in that the groups Z(--X--)_(n)are to be introduced into the formula scheme instead of the groups CH₂CH₂ (--O--)₂, with --X-- corresponding to the bridges --S-- or --NR¹ --.

As starting products there may be used compounds of the formula II, inwhich X is the same (for example, polyalcohols, polyphenols, polyamides)or different (aminoalcohols, aminophenols, mercaptophenols), and alsomixtures of compounds of formula II may be used as starting compounds inorder to obtain mixtures of compounds of formula I. However, it is alsopossible to use mixtures of compounds of formula III and/or V asstarting products, thus obtaining the corresponding mixtures of formulaI or mixed added compounds of formula I. It is also possible to use forthe oxalkylation reactions the compounds V, i.e. alkylene carbonates, aswell as the compounds IV, i.e. alkylene oxides, at the same time. Inthis manner the positive solution properties of the alkylene carbonatesmay be connected with the more favorable price of the alkylene oxides.

In correspondence with the general reactivity of basis compounds havingactive hydrogen atoms (formula II) with phospholanes of the formula IIIand subsequently with alkyl carbonates of the formula V, in whichprocess finally a compound of formula II is again obtained, there may bementioned very extensive classes of compounds as basis substances forthe process of the invention, which comprise a large part of organicchemistry. Although the possibilities of reaction are far more varied,the invention is to be limited for formal reasons to the basic classesof compounds II Z(--XH)_(n) generally defined above.

As basic classes of compounds II that can be obtained most easily thereare preferred hydroxyl compounds, if --X-- represents an --O-- bridge.Of the monovalent organic hydroxyl compounds with n = 1 there arementioned, for example, all easily accessible aliphatic straight-chainand branched alcohols having from 1 to about 18 carbon atoms. The mostimportant are, for example, methanol, ethanol, n-propanol, i-propanol,n-butanol, sec.-butanol, n-hexanol, 2-ethyl-butanol-1, n-octanol,2-ethyl-hexanol-1, n-dodecanol, n-hexadecanol, n-octadecanol, thealcohols having from 1 to 4 carbon atoms being preferred. Polyhydricalcohols with n = 2-6 are even more favorable than monofunctionalalcohols.

Of the polyvalent aliphatic polyols with n = 2-6 there are mentioned,for example: ethylene-glycol, 1,2-propylene-glycol,1,3-propylene-glycol, 1,4-butane-diol, neopentyl-glycol,1,6-hexane-diol, glycerol, trishydroxy-methylethane,trishydroxy-methylpropane, pentaerythritol, sorbitol, mannitol.Preference is given particularly to glycerol, pentaerythritol andsorbitol.

Of unsaturated alcohols there may be mentioned, for example,n-butene-2-ol-1, 1,4-butene-diol and allyl alcohol, with 1,4-butene-diolbeing preferred as bivalent alcohol.

Of the numerous compounds in which in an aliphatic hydrocarbon radicalone or several --CH₂ -- groups are replaced by ether bridges --O--,there are suitable, for example, the reaction products of monovalentalcohols with one or several molecules of alkylene oxides or alkylenecarbonates, such as, for example: 2-Methoxy-ethanol, 2-ethoxy-ethanol,2-n-butoxy-ethanol, 2-(2'-ethyl-hexyloxy)-ethanol,2-n-dodecyloxy-ethanol, moreover, the reaction products of 1 mole ofmethanol, 1 mole of ethanol or 1 mole of isopropanol and 2 moles ofethylene oxide or alkylene carbonate, i.e. methyl-diglycol,ethyl-diglycol and/or isopropyl-diglycol, furthermore, the reactionproducts of 3 to 7 molecules of ethylene oxide or ethylene carbonatewith 1 mole of methanol, ethanol, isobutanol.

Appropriate reaction products of ethylene oxide and bivalent alcoholsare, for example, the so-called diglycol and triglycol and thehigh-molecular weight reaction products of ethylene oxide and/orethylene carbonate with water or ethylene-glycol having up to 18 carbonatoms, the so-called polyethylene-glycols having various molecularweights up to a medium molecular weight of 400, especially diglycol andtriglycol, and there are suitable, furthermore, for example the additionproducts of 1 to 6 molecules of ethylene oxide and/or ethylene carbonatewith tri- or polyhydric alcohols (n = 3-6), such as glycerol,trishydroxy-methyl-propane, pentaerythritol, etc.

Besides reaction products of ethylene oxide and/or ethylene carbonatewith mono- or polyhydric alcohols there may also be mentioned reactionproducts of mono- and polyhydric alcohols with other 1,2-alkylene oxidesand/or 1,2-alkylene carbonates, such as in particular, 1,2-propyleneoxide, 1,2-propylene carbonate or epichlorhydrin, as well as thereaction products of ethylene oxide and/or ethylene carbonate withpoly-1,2-propylene-glycols which are prepared as surface-activecompounds in a wide variation, as has already been known. There arementioned in particular corresponding poly-1,2-propylene-glycols andcorresponding addition products of ethylene oxide and/or ethylenecarbonate to (poly)-1,2-propylene oxides.

Besides by --O-- bridges, the hydrocarbon chain of aliphatic hydroxylcompounds may also be interrupted by other hetero atoms, for example, bythe elements N, S and/or P or carboxylic acid ester groups. Thesecompounds may be obtained in a particularly easy manner, for example, byreacting one or several molecules of 1,2-alkylene oxides and/or1,2-alkylene carbonates with ammonia, primary or secondary amines,hydrogen sulfide, mercaptans and with oxo-acids of phosphorus, (C₂-C₆)-carboxylic acids and/or dicarboxylic acids.

Of these reaction products with 1,2-alkylene oxides and/or 1,2-alkylenecarbonates, there may be mentioned, for example:

With N in the molecule: the tertiary alkanolamines, such astri-ethanolamine, methyl-diethanolamine, n-butyl-diethanol-amine,tetra-hydroxyethyl-ethylenediamine,pentahydroxyethyl-diethylene-triamine, n-dodecyl-diethanolamine,dimethyl-ethanol-amine, n-butyl-methyl-ethanolamine,di-n-butyl-ethanolamine, n-dodecyl-methyl-ethanolamine and thecorresponding high-molecular-weight reaction products of these tertiaryamines with ethylene oxide and/or ethylene carbonate or propylene oxideand/or propylene carbonate having a total number of carbon atoms of upto 18 per molecule.

With S in the molecule: Bis-(2-hydroxyethyl)-sulfide,bis-(2-hydroxy-propyl)-sulfide, bis-(2-hydroxyethyl)-sulfone and theirreaction products with a further amount of ethylene oxide and/orethylene carbonate or propylene oxide and/or propylene carbonate havinga total number of carbon atoms of up to 18 C-atoms per molecule.

With P in the molecule: Neutral reaction products of 1,2-ethyleneoxides, such as ethylene oxide, propylene oxide, epichlorhydrin,especially ethylene oxide and/or, for example, ethylene carbonate withmono- and polyvalent alkane-phosphonic acids having from 1 to 18 carbonatoms, for example, with n-butane-, isobutane-, 2-ethyl-hexane-,n-octane-, decane-, dodecane-, tetra-decane-phosphonic acid, especiallywith methane-, ethane, propane- and vinyl-phosphonic acid and1,2-ethane-diphosphonic acid, furthermore, with mono- or polyvalentdi-alkyl-phosphinic acids, such as methyl-butyl-phosphinic acid,methylene-n-octyl-phosphinic acid, methyl-n-dodecyl-phosphinic acid andin particular dimethyl-, ethyl-methyl-, methyl-propyl-,methyl-vinyl-phosphinic acid and ethane-1,2-bis-(methyl-phosphinicacid), and additionally reaction products of 1 to 2 moles of alkyleneoxide and/or ethylene carbonate with monovalent aliphatic carboxylicacids, such as crotonic acid, especially acetic acid, propionic acid,butyric acid and polyvalent aliphatic carboxylic acids, such as succinicacid and adipic acid.

The reaction of the various phosphorus-containing acids and ofcarboxylic acid in particular with alkylene oxides and/or alkylenecarbonates may also be effected in the presence of the phosphoruscompounds III. In the course of this process, intermediate productscontaining hydroxyl groups are formed in the reaction mixture, theformer products acting as basis compounds II Z(--XH)_(n) and reactingwith the compounds III present in an excess amount and with furthermolecules IV to give the final products. Therefore, it is also possibleto use carboxylic acids or -- for example -- phosphorus-containing freeacids without additional --XH-groups directly as starting compounds.This method often simplifies the process considerably.

Thus, there are to be mentioned as possible starting compounds yieldingthe basis compounds II in situ for this process in particular the freecarboxylic, phosphonic and phosphinic acids for example, which maycontain hydroxyalkyl groups and which may also include, besides a freeacid group, one or several OH groups, such as, for example, glycolicacid, 2-hydroxy-propionic acid, lactic acid, 2-hydroxyethyl-phosphonicacid, hydroxymethyl-phosphonic acid, 2-hydroxyethyl-methyl-phosphinicacid, etc. However, it is also possible to obtain further compounds ofthe formula II by using anhydrides of phosphonic, phosphinic, carboxylicacids or dicarboxylic acids as starting products, by reacting the samewith compounds of the formula II and subsequently oxalkylating them withcompounds of the formulae IV and V.

In the total balance, one more molecule of the 1,2-alkylene oxides IVand/or 1,2-alkylene carbonates V is needed altogether per free acidgroup or acid group to be set free.

Besides these hydroxyl compounds which may very easily be obtained byoxalkylation reactions and which include the hetero-atoms N, S and P,numerous further compounds with hydroxyalkyl groups and, optionally,with said heteroatoms and/or carboxylic acid ester groups in thehydrocarbon chain are also appropriate, such as, for example,oligo-condensation products being formed by the reaction of dicarboxylicacids or dicarboxylic acid anhydrides with polyhydric alcohols,moreover, glycolic acid-methylester, 2-hydroxyethane-carboxylicacid-ethylester, etc.

There are also suitable, for example, hydroxymethane-phosphonicacid-dimethylester, 2-hydroxyethane-phosphonic acid-diethylester,3-hydroxypropane-phosphonic acid-di-n-butylester, etc. and analogouscompounds of the phosphinic acid series, such ashydroxymethyl-methyl-phosphinic acid-methylester,2-hydroxyethyl-methyl-phosphinic acid-ethylester,3-hydroxypropyl-methyl-phosphinic acid-2'-ethyl-hexylester,hydroxymethyl-dimethyl-phosphine oxide,2-hydroxyethyl-dimethyl-phosphine oxide.

All the analogous aliphatic hydroxyl compounds mentioned above or notmentioned before may be substituted by the halogen atoms chlorine,bromine, fluorine, especially by chlorine and bromine. There are to bementioned, for example, the easily accessible compounds indicated in thefollowing, which are interesting due to their favorable flameproofproperties: 2-Bromoethanol,2,3-dibromopropanol-1,2,3-dibromo-butanediol-1,4, dibromo-succinicacid-bis-(2-hydroxyethyl)-ester, 2-dibromopropane-phosphonicacid-bis-(2-hydroxyethyl)-ester, 2-hydroxyethane-phosphonicacid-bis-(2,3-dibromopropyl)-ester, moreover, chloroethanol,2,3-dichloro-propanol-1, 1,3-dichloro-propanol-2,2,3-dichloro-butanediol-1,4, 2-hydroxyethane-phosphonicacid-bis(2,3-dichloropropyl)-ester, 1-chloro-vinyl-phosphonic acid-bis(2-hydroxyethyl)-ester.

The compounds having reactive groups, in which one or several --X-- areidentical with a --NHR₁ -bridge, include monovalent aliphatic primaryand/or secondary amines whose hydrocarbon radicals may be interrupted byoxygen, carboxylic acid ester groups or by sulfur or phosphorusfunctions and may be substituted by hydroxyl groups, such as, forexample, methylamine, ethylamine, isopropylamine, n-butylamine,2-ethyl-hexylamine, dodecylamine, octadecylamine etc., ethylamine,diethylenetriamine, 1,4-butylene-diamine, etc., dimethylamine,diethylamine, di-n-butylamine, methyl-n-dodecylamine,methyl-n-octadecylamine, di-n-dodecylamine, etc.,N,N'-dimethyl-ethylenediamine, furthermore, ethanolamine,isopropylamine, n-octyl-2-hydroxy-propylamine,n-tetra-2-hydroxy-ethylamine, N,N'-bis(2-hydroxyethyl)-ethylene-diamine,mono-2-hydroxy-propyl-diethylene triamine, etc., also the reactionproducts of mono- or polyvalent glycidyl compounds with ammonia orprimary amines, for example,n-butyl-3-amino-2-hydroxy-1,2-bis-(3-methylamino-2-hydroxypropyl)-etheretc., for example, so-called diamino-polyethyleneglycols, i.e.polyethylene-glycols of a different molecular weight of up to about 600,in which the terminal hydroxy groups have been replaced by --NH₂, andfor example the bis-(3-amino-2-hydroxy-propyl)-ethers ofpolyethylene-glycols having a different molecular weight of up to about500.

Of esters with amino groups there are mentioned the esters of2-amino-carboxylic acid, of protein units, such as aminoaceticacid-methylester, α-aminopropionic acid-ethylester, α-ε-diaminocaproicacid-isopropylester, etc. It is also possible to use free amino acids inthe reaction mixture because of the conversion of the free carboxylgroups into hydroxyl intermediate products.

As amine having a phosphorus function there may be used, for example,3-amino-propyl-dimethyl-phosphine oxide which may easily be obtainedfrom allylamine and dimethyl-phosphine oxide.

Of compounds in which --X-- represents the bridge --S-- there may bementioned, for example, hydrogen sulfide and aliphatic compounds havingmercapto groups, such as methyl-, ethyl-, n-butyl-, n-octyl-,n-dodecyl-mercaptan, β-mercapto-ethanol, thioglycolic acid-ethylesterand also, for example, thioglycolic acid, since the carboxyl group isprimarily converted into the 2-hydroxy-alkylester.

Of the derivatives of cyclohexane, which are substituted by n-XH-radicals, there are to be mentioned, above all:

Cyclohexanol, methylcyclohexanol, 1,4-dihydroxy-cyclohexane,1,3-dihydroxy-cyclohexane, 1,4-diamino-cyclohexane.

There is also a large selection of appropriate aromatic compoundscarrying n --XH-radicals. If --XH-- stands for --OH, there may bementioned all the so-called phenols in the broader sense, such as, forexample, phenol, pyrocatechol, resorcinol, hydroquinone, pyrogallol,oxyhydroquinone, phloroglucinol, the various tetra- andpentahydroxy-benzenes, hexaoxybenzene, α-naphthol, β-naphthol, moreover,hydroxynaphthalenes having more than one hydroxy group, such as, forexample, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-,2,3-dihydroxy-naphthalenes, moreover, 4-hydroxydiphenyl,4,4'-dihydroxy-diphenyl, and -- due to its favorable price -- especially2,2-bis-(4-hydroxyphenyl)-propane and4,4'-bis-(4-hydroxy-phenyl)-methane. Also partially etherifiedpolyvalent aromatic hydroxyl compounds, such ashydroquinonemonomethylether, resorcinol-monoethylether, etc. areappropriate.

Owing to their favorable influence of the flameproof properties,aromatic chloro- and especially bromo-hydroxy-compounds are ofparticular interest, such as, for example, 2,4,6-tribromo-phenol,pentabromo-phenol, 2,4,6trichlorophenol or pentachloro-phenol and2,2-bis-(4-hydroxy-3,5-dibromo-phenyl)-propane.

Moreover, there are suitable aromatic hydroxyl compounds having alkylchains with a total of up to 18 carbon atoms, such as o-, m- and/orp-cresol, thymol, 4-tert.-butyl-phenol, 2,4,6-tri-tert.-butyl-phenol,n-nonylphenol, isononylphenol, isotridecyl-phenol, etc.

Among the aromatic compounds, there are preferred all the aromaticcompounds having alcoholic hydroxyl groups, such as, for example, benzylalcohol and all 2-hydroxyalkyl-ethers or -esters which are formed byoxalkylation reactions of phenolic hydroxy groups or of aromaticcompounds containing carboxylic acid, phosphonic acid or phosphinic acidradicals, with compounds of the formulae IV or V.

For the preparation of aromatic starting compounds II with alcoholichydroxyl groups there may therefore be mentioned, besides the aromaticcompounds with phenolic hydroxyl groups already mentioned above, for thereaction with 1,2-alkylene oxides IV or 1,2-alkylene carbonates V,especially for example aromatic mono- and dicarboxylic acids, such asbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid,1-naphthalene-carboxylic acid, naphthalene-carboxylic acid, the variousnaphthaline-dicarboxylic acids, but also aromatic hydroxy-carboxylicacids, such as the three different hydroxy-benzoic acids, the differentnaphthol-carboxylic acids, 4,4'-diphenyl-dicarboxylic acid, etc.

There are also suitable, for example, all the other aromatic carboxylicacids containing bromine, chlorine or fluorine, which are derived frombenzene and naphthalene, such as - in particular-tetrabromo- and/ortetrachloro-phthalic acid and/or the anhydrides thereof. In this case,too, the reaction with compounds IV or V may be effected already in thepresence of the compounds III, so that a corresponding process step maypossibly be avoided, especially in the lay-out of technical processes.

In the same manner, aromatic phosphonic and/or phosphinic acids, such asbenzene-phosphonic acid, 1,3- and/or 1,4-phenylene-diphosphonic acid,phenyl-methyl-phosphinic acid, 1,3-and/or1,4-phenylene-bis-(methyl-phosphinic acid) may either be convertedbefore into the corresponding 2-hydroxyalkylesters by a reaction withthe 1,2-alkylene oxides IV and/or 1,2-alkylene carbonates V, or theseacids and/or the many other suitable acids that have not been mentionedcan be reacted in the reaction mixture directly with the1,2-alkylene-oxides IV and/or 1,2-alkylene-carbonates V and thecompounds III.

However, appropriate aromatic compounds with alcoholic hydroxyl groupsmay also be obtained by previous reactions of aromatic amines ormercapto compounds with 1,2-alkylene oxides and/or1,2-alkylene-carbonates.

For these reactions, the following aromatic amines and/or mercaptans maybe used in the form of compounds II Z(--X--H)_(n). Naturally, they canalso be used directly, i.e. without previous oxalkylation, due to their--XH-groups.

As compounds to be used which contain aromatic amino groups, there areto be mentioned, for example:

Aniline, methylaniline, o-, m-, p-phenylene-diamine, the various o-, m-,p-toluidines and -anisidines, -aminophenols, -aminobenzoic acids,-aminobenzene-sulfonic acids, 1- and/or 2-naphthyl-amines, the variousamino-naphthols, moreover, 4,4'-diaminodiphenylmethane, 4,4'-benzidine,the suitable chloro- and/or bromo-anilines and especially2,4,6-tribromo-aniline, etc., but also phenylalkylamines, such as, aboveall, benzylamine or methyl-benzylamine and dibenzylamine.

As aromatic mercapto compounds there may be cited, for example:

phenylmercaptan, p-toluyl-mercaptan and/or 2-naphthyl-mercaptan, etc.

The suitable compounds III having the general formula ##STR16## include,for example, 2-methyl-, 2-ethyl-, 2-n-propyl-, 2-isobutyl-, 2-vinyl-,2-chloromethyl-, 2-phenyl-, 2,3-dimethyl-, 2-methyl-3-ethyl,2-methyl-3-butyl-, 2,4-dimethyl-, 2-methyl-4-ethyl-, 2-phenyl-4-methyl-,2,3,4-trimethyl-, 2,3,4-triethyl-, but in particular - due to its easypreparation - 2-methyl-2,5-di-oxa-1,2-oxa-phospholane.

Appropriate 1,2-alkylene oxides of the formula IV are, for example,1,2-butylene-oxide, 2,3-butylene oxide, but preferably epichlor hydrin,propylene oxide and especially ethylene oxide. Suitable1,2-alkylene-carbonates of the formula V are, for example, propylenecarbonate, 1,2-butylene-carbonate, 2,3-butylene-carbonate,3-chloropropylene-carbonate and, preferably ethylenecarbonate.

The use of inert solvents and/or diluents is in most cases not required.However, there may be added, for example, acetone, methyl-ethyl-ketone,acetonitirle, 1,2-dichloroethane, benzene, toluene, xylene,chlorobenzene, but above all dioxane, if necessary, without any harm, asdiluents and/or solvents, and these agents can be eliminated again byway of distillation still prior to the complete reaction with the1,2-alkylene-carbonates V or at the very termination of the reaction.

The reaction temperatures for compounds II and III are in the range offrom 0° to 180° C or higher, for example up to 250° C, preferablybetween 20° and 150° C, especially between 80° and 150° C. The reactionwith the 1,2-alkylene-carbonates V is effected at a temperature ofbetween about 80° and 250° C, preferably from 160° to 220° C, and withthe 1,2-alkylene oxides at a temperature of from 80° to 180° C,preferably from 100° to 150° C. The reaction may be carried out stepwisein a way that at first 1 mole of the compounds II with n -X-H-groups isreacted with 1 to n moles of the "phospholanes" III and subsequently atfirst the same number of moles of compounds III and/or V act upon themixture, until the acid number has been reduced to practically O.Afterwards the further moles of phospholane III and compounds IV and/orV are added in turns up to the desired final amount of n × m moles ofthe phhospholanes III and/or at least n × m moles of compounds IV and/orV, if neutral esters (n × m) are to be obtained, or up to n × m (m+1)moles of phospholanes III and n × m moles of compounds IV and/or V, ifproducts are desired that are still acid.

According to a preferred variant of the process, however, all n × (m+r)moles of the phospholanes III are introduced together with one mole eachof the substances II containing n --X--H-- groups and -- if acid finalproducts (r=1) are to be obtained -- together with n × m moles of the1,2-alkylene-carbonates V and/or -- to obtain neutral final products(r=0) -- together with at least n × m moles of the compounds of formulaeIV and/or V.

Due to by-reactions and impurities of the basis compounds II, thephospholanes III and/or the alkylene carbonates, it may be possible inmay cases that more starting molecules are present than have beenintended. This has the effect in some cases that the contents ofhydroxyl groups found are slightly higher than have been calculated.

Depending on the value of n and/or m and on the type of compoundZ(--X--H)_(n) present, the compounds obtained are colorless and/or of amore or less yellowish shade and of a different consistency. If n equals1, --X-- is oxygen or --S--, R₃ represents a lower alkyl radical and R₄and/or R₅ are either also a lower alkyl radical or hydrogen, viscousliquids are obtained; if n is 2, viscous oils are present in most cases,and if n is 2, there are predominantly solid viscous masses, which areall well soluble in water, however.

If the molecular weight is increased by long chains, i.e. by high valuesof m, the viscosity is also increasing considerably.

Most compounds having NR₁ -bridges are also solid, but water-soluble,with a varying water-solubility depending on the nature of Z. Aromaticbasis substances, too, become water-soluble with values of m exceedingapproximatelay 3 or may be dispersed in water, even if they contain inaddition other groups which strongly reduce the water-solubility, forexample, halogen atoms, fluorine, chlorine or bromine.

Due to their relatively high phosphorus content, the compounds offormula I, especially the neutral and polyvalent compounds, are verywell suitable as starting products for flameproofing agents or, incombination with cross-linking substances, directly as flameproofingagents that are fixable while being fast to washing, for example fortextile goods. The application of these compounds is effected byimpregnation of the textile material with a bath containing a compoundof formula I, cross-linking compounds and a cross-linking catalyst, andby a subsequent cross-linking by a heat treatment.

As cross-linking components there may be mentioned polyfunctionalN-methylol compounds, for example, derivatives of amino-1,3,5-triazines,such as trimethylol-melamine, hexamethylol-melamine,trimethylol-melamine-trimethylether,hexamethylol-melaminepentamethylether,trimethylol-melamine-triisobutylether, dimethylolaceto-guanamine,moreover, derivatives of urea, such as dimethylol-urea,dimethylol-urea-dimethylether, dimethylol-urea-dibutylether,dimethylol-cycloethylene-urea, dimethylol-cyclo-propyleneurea,dimethylol-4-methoxy-5-dimethyl-propylene-urea,dimethylol-5-hydroxypropylene-urea,1,3-dimethylol-4,5-dihydroxy-imidazolidone-(2),1,3-dimethylol-5-hydroxyethyl-hexahydrotriazine-on-(2), dimethylol-uroneand dimethylol-carbamates, such as dimethylol-methyl-carbamate,dimethylol-hydroxyethylcarbamate and dimethylol-methoxy-ethylcarbamate.

Interesting compounds which have proved to be particularly useful arethe melamine derivatives, for example, trimethylolmelamine-trimethylether or hexamethylol-melamine-pentamethylether.

As catalysts which show their effect in the acid pH range, there aregenerally added from about 0.2 to 5% by weight, preferably from 0.4 to3% by weight, of inorganic or oganic acids or their salts which set theacid free by hydrolysis or by a thermal treatment, for example, sulfuricacid, hydrochloric acid, phosphoric acid, trichloroacetic acid, maleicacid, tartaric acid, citric acid, acetic acid, or the salts thereof withammonia, amines or polyvalent metals, preferably salts of strong acidsor of medium strength, such as ammonium sulfate, ammonium chloride,mono- and diammonium oxalate, ammonium nitrate, magnesium chloride,aluminum chloride, zinc chloride, zinc nitrate, zinc fluoroborate,2-amino-2-methyl-propanol-hydrochloride.

The cross-linking catalysts may be added to the finishing baths bythemselves or in admixture with one another. These -- preferably aqueous-- finishing baths contain generally from 2 to 5% by weight, preferablyfrom 2.5 to 4.5% by weight, of compounds of formula I, moreover, from 5to 10% by weight, preferably from 7 to 9% by weight, of cross-linkingsubstances as indicated above, furthermore from 0.2 to 5% by weight ofcross-linking catalysts, as well as, optionally, from 5 to 25% by weightof high polymers, preferably in the form of dispersions.

The above-described phosphorus-containing compounds of formula I arewater-soluble products or products that may be dispersed in water. Theyare added to the finishing baths in this form.

A special advantage of the compounds of the invention is to be seen alsoin their high stability, which involves a capacity of being stored for along time also of aqueous concentrates as well as of aqueous finishingbaths which already contain crosslinking agents and catalysts.

As textile fiber material there may be mentioned fibers and/or fabricson the basis of native or regenerated cellulose or their mixtures. Verygood permanent flameproof effects are obtained on synthetic fibermaterial or mixed fibers. As synthetic or mixed fiber material there aresuitable, above all, non-woven fabrics, for example, needle felts forwall and floor coverings, textile wall coverings and air filters havinga different composition, for example, needle felts ofpolyester-/polyamide-6-fibers in a 50/50 ratio, 100% polyamide fibers,100% polyester fibers, polyamide fibers and viscose staple fibers in a50/50 ratio, polyester fibers with viscose staple fibers in a 50/50ratio or in a 75/25 ratio, polyamide/polyacrylonitrile/polyester fibersin a 50/25/25 ratio, glass fibers with polyester fibers in a 75/25ratio, wool and polyamide fibers in a 50/50 ratio.

Suprisingly, the above-described phosphinic acid esters are alsoappropriate for the flameproof finishing of textile material made ofpolypropylene fibers or their mixtures with other synthetic or native orregenerated cellulose fibers, which could not be obtained so far in asatisfactory manner on the basis of phosphonic acid derivatives.

The process of the invention to impart a flameproof finish to textilematerials is carried out under application conditions as they are commonin the textile industry. The fabrics and/or needle felts are treatedwith the aqueous finishing baths on a two-roll and/or three-roll paddingmangle, are squeezed off and subjected to a drying and/or condensationprocess. Fleeces that are bound by binding agents are either alsofinished on a padder or are hardened by being sprayed or foamed with thebinding mixture.

For the flameproof finishing of cellulose fiber fabrics, the thermaltreatment is carried out preferably in two steps. The material is atfirst dried at a temperature of more than about 50° C, preferably atabout 100° C to 120° C, in order to eliminate the water to a residualvalue of from about 4 to 8%, and subsequently the condensation isallowed to take place at a temperature of from about 140° to 180° C, forapproximately 7 to 3 minutes.

The flameproof finishing of needle felt covering material may also beeffected according to the two-step process. However, in this case thecross-linking is preferably performed in a one-step drying and/orcondensation process at a temperature of from about 120° to about 180°C, predominantly at 145° to 160° C. The heat treatment lasts for about10 to about 60 minutes on an average, preferably from 20 to 30 minutes.The action of heat takes place in drying chambers, on stenter frames,hot flues or condensing stenters.

Further agents may be added to the finishing baths, such as textilesofteners, products imparting water-repellent properties, productsimparting oil-repellent properties, or also antimicrobial finishingproducts.

In order to improve the feel of cellulose fiber fabric, to ensure a goodretention of shape, to improve the fasteness to rubbing and crushing ofneedle felt covering material, high polymer plastic materials may beadded to the finishing baths, preferably in the form of plasticdispersions, for example on the basis of polyvinyl acetate, polyvinylacetate with plasticizers, such as dibutyl-phthalate, copolymers ofvinyl acetate with maleic acid-dibutylester, copolymers of acrylicacid-butylester with N-methylolacrylamide and acrylic acid, copolymersof acrylic acidbutyl-ester, N-methylolacrylamide and/orN-methylol-methacrylamide and acrylic acid, copolymers of acrylicacid-butylester, methacrylic acid-methylester andmethylol-methacrylamide, copolymers of acrylic acid-butylester,acrylonitrile, N-methylolacrylamide and metahcrylic acid, copolymers ofacrylic acid-butylester, acrylic acid-ethylester, acrylonitrile,N-methylol-methacrylamide and acrylic acid, copolymers of acrylicacid-butylester, styrene, acrylonitrile and N-methylol-methacrylamide,copolymers of N-methylol-methacrylamide and butane-diol-diacrylate,acrylic acid-methyl-ester and acrylic acid-butylester, copolymers ofethyl-acrylate, acrylonitrile and N-methylolacrylamide, copolymers ofbutylacrylate, vinyl acetate with N-methylolacrylamide, copolymers ofbutylacrylate, acrylonitrile and N-methylolacrylamide, copolymers ofstyrene, butylacrylate and acrylic acid, natural latex or syntheticlatices from styrene with butadiene.

Preferred polymer dispersions are polyvinyl acetate dispersions (of 50%strength), copolymers of vinyl acetate with maleic acid-dibutylester,for example in a ratio of 77/23 (about 50% strength), copolymers andstyrene/butylacrylate/acrylonitrile/methacrylic acid/acrylamide, forexample in a ratio of 16:61:25:2:1 or 25:53:25:2:1, copolymers ofethylacrylate/acrylonitrile/N-methylol-acrylamide 6:3:1, copolymers ofbutylacrylate/vinyl acetate/N-methylolacrylamide 35:55:10, furthermore,graft polymers (partially saponified), such as 50% polyvinyl alcohol,25% polyvinyl acetate, 25% polyethylene oxide or butadiene-styrene latex(of about 50% strength), for example in a ratio of 40:60, 60:40 or35:60 + 3.5 acrylic acid.

As compared with the commercial flameproofing agents on the basis of3-(dimethyl-phosphono-)-propionic acid-amide, the products of theinvention show great advantages especially with regard to permanence, tomention in particular the flameproof effect on polypropylene fibers ormixed fiber material and the excellent permanence especially afterseveral commercial fine washings or shampooings.

Due to the very good flameproof effect of the compounds of the generalformula I, the products may also be applied via the carpet back or viathe pre-coating, and an ordinary bath finishing is therefore no longerrequired. This fact is of particular importance, since in the ordinarybath impregnation the pile thread, too, gets into contact with theflameproofing agents, cross-linking agents, binding agents on the basisof plastic dispersion and catalyts. In this treatment of the carpetpile, the flameproofing agents and the other components of the treatmentbath are found on or between the pile threads, thus leading toagglutination. The individual thread of the pile should remain loose,however. Generally, an agglutination of the pile also results in astronger soil deposition. Besides, the flameproofing agents may slowlybe worn out by walking on the carpet.

The finish thus obtained is marked by its very good flameproofproperties as well as by its very good permanence, for example, inshampooing and carpet washing processes.

The basic fabric of the carpets may consist of cotton, jute, viscosestaple fiber, wool or synthetic fibers on the basis of polyamide orpolyester, polypropylene or a mixture of the same, or of glass fibers.Needled fleece materials of polyester or polypropylene fibers are alsoexcellently suitable for the process according to the invention.

The binding of the pile threads of a tufted material into the basicfabric, which may consist of natural or synthetic fibers or of needledfleeces of synthetic fibers, is effected by the so-called pre-coatingwith the commercial 40 to 50% plastic dispersions of the kind mentionedabove.

Plastic dispersions of this nature are also used as back finish forwoven carpets to impart a good feel in the hardening of the carpet.

Generally, a back coating with natural latex or synthetic latexdispersion, for example on the basis of butadiene and styrene 40:60 or60:40, is effected subsequently in the case of tufted carpets.

As pile threads for tufted as well as woven carpets there may bementioned fiber material of wool, polyamide, polyester andpolyacrylonitrile. Fiber material of wool, polyamide or polyesterthreads having the common height of cut of 4 to 12 mm is preferablyused.

The finishing baths for the pre-coating as well as for the back coatingin the case of woven carpets contain in addition thickening agents.

As is already known, the thickening agent serves the purpose to put thefinishing compositions into a physical state which prevents theimpregnation baths from penetrating into the pile threads duringapplication, thus agglutinating the same. As thickeners, there aresuitable water-soluble hydroxyethylcelluloses, methyl celluloses,carboxylmethyl celluloses, water-soluble starch products, partiallyetherified or etherified starch products, polyvinyl alcohols, and thesodium or ammonium salts of alginic acid.

The pre-coating or the carpet back coating for woven carpets may besidesbe filled with chalk in a common manner.

The process for producing a flameproof finish in pile carpets by acarpet back treatment -- a pre-coating or back coating -- is carried outunder the application conditions, as they are common in textileindustry.

The pre-coating composition or the back finish in the case of wovencarpets which contain the flameproof compound of formula I, thecross-linking agent and the catalyst, are applied by means of a skyingdoctor, a rubber squeeze or a cylinder doctor. Subsequently the materialis dried and/or hardened on the stenter frame, in gelatinating or dryingchannels or in cylinder drying machines at a temperature of from 125° to150° C. The dwelling time depends on the thickness of the carpets and isin the range of from 5 to 20 minutes, preferably 7 to 10 minutes. Theback coating for tufted carpets is generally carried out by foaming thebinding agent which contains the three components for the flameprooffinish mentioned above. As cross-linking agents and catalysts there maybe mentioned for this purpose the products that have been indicatedfurther above.

When the burning and/or fire behavior of a tufted material is tested,which material has been finished with a flameproof agent according tothe invention via the pre-coating and in addition is provided with alatex back coating, an excellent flameproof effect is surprisingly foundfor the entire carpet. The flameproof pre-coating forms a barrier layertowards the latex back so that the latter cannot be inflamed. It istherefore sufficient to incorporate the flameproof component into thepre-coating. In this case the latex back and the pile fibers do notrequire a flameproof finish. The compounds of the general formula I aremarked by their high stability.

The said stability permits a prolonged storage of the finishing pastesready to apply which contain, besides the flameproof agent, thecross-linking agent, the catalyst, the thickener and a latex dispersion.This flameproofing process is also distinguished by the fact that underthe action of flames, no aggressive vapors in the form of hydrogenchloride or hydrogen bromide are formed, as this is the case to a largeextent, if as flameproofing component there are used products on thebasis of paraffin chloride, PVC, inorganic or organic bromine compounds.

In the following Examples there have been described at first twopreparation processes to be applied generally for the reaction withalkylene oxides. The Examples carried out according to these processesas well as their results have been summarized in Tables A and B. In theApplication Examples the use of the compounds thus obtained for textilefinishing operations have further been indicated.

The Tables contain in their first column the serial number of theExamples, in the second column the chemical formula of the basiscompound used. The third column gives the valency n of this compound,and the following columns 4 to 6 show the amounts used of the threereactants as well as the pertinent mole numbers. As compound III thereis generally used 2-methyl-2,5-dioxo-1-oxa-phospholane-2. In Examples(34)⁺ and (35)⁺, compound III stands for the corresponding2,4-dimethyl-phospholane and in Example (61)⁺ for the corresponding2-phenyl-phospholane.

As alkylene oxide IV there is generally used ehtylene oxide; in Example(36).sup.× use is made instead of propylene oxide, and in Examples (37to 40)⁺, of epichlorhydrin.

Column 7 contains once again a summary of the molar ratio figures,column 8 shows the amount and definition of a catalyst used, and column9 gives the reaction temperature and/or time. In column 10, the acidnumber found of the final product has been indicated. As far as theconsistency at room temperature (column 12) permitted a measuring of therefractive index, this latter value has been shown together with thecorresponding temperature ( ° C) in column 11.

The yields and the phosphorus content of the products obtainedpractically correspond to the theoretical values and have thus not beenincluded, for reasons of clearness.

In Example (30), 50 g of dioxan (indicated in column 8) were used asco-solvent.

E X A M P L E S A. General preparation method for Examples 1 through 50

(Table A)

At a reaction temperature of from about 80° to 130° C, a moles (column4) of the basis compounds of the formula II were introduced within about5 to 20 minutes, optionally while drawing off the reaction heat, into a× n × m moles (column 5) of the phospholanes III. In this case, n standsfor the number of --XH-groups (column 3) present in the basis compounds,and m is the number of moles used per --XH-group of compound III (column7). Subsequently, a × n × m moles were either added at once, in the caseof hardly volatile alkylene oxides IV, and were reacted during thereaction time, or at least a × n × m moles were introduced in a gaseousstate, without pressure, during the reaction time, in the case of morevolatile alkylene oxides, especially with ethylene oxide which is mostlyused, or were slowly added dropwise during the reaction time, whileusing a reflux condenser, in the case of other alkylene oxides having alow boiling point, for example, propylene oxide. In this process the gasintroduction rate and/or dropping rate was controlled in accordance withthe chemical reaction, so that practically no alkylene oxide was lost.The action of the easily volatile alkylene oxides was allowed tocontinue until the respective so-called acid number (consumption of mgof KOH per g of substance), which was determined in a 1:1 methanol-watermixture with phenolphthalein as indicator, had been reduced to less thanabout 12. Subsequently, all portions which were volatile under theseconditions were eliminated under a reduced pressure of about 20 to 100Torr at a temperature of from about 80° to 130° C. If alkylene oxideswere used which were sufficiently volatile, the number of moles used wascalculated from the difference between the input weight and the outputweight. In order to characterize the compounds, the IR and the NMRspectrums were taken, the refractive indices (if possible), the acidnumbers and the phosphorus contents were determined, with the latternaturally being almost fully in accordance with the contents calculatedtheoretically from the number of moles of III. The products obtainedshowed in the NMR spectrum characteristic multiplets at δ = 3.5 - 3.9and δ = 3.9 - 4.5 which were lacking in the phospholanes used asstarting compounds.

B. General preparation method for Examples 51 through 62

(Table B)

For the preparation of basis compounds of formula II in situ (cf.description on page 5), the same process as given in method A wasapplied with the difference that instead of the compounds of formula II,use was made of a moles of phosphonic, phosphinic or carboxylic acids asstarting compounds V (= preliminary stage) with s acid final groups andn' final groups of types (XH) of the invention in the molecule. In themixture of these compounds with the corresponding phospholane andalkylene oxide, a moles of compounds of formula II with n = n' + s(column 3) were then formed in the first reaction step by the additionof one alkylene oxide each to an acid final group, which productscontinued to react, as has been described under A, with the phospholaneof formula III and further alkylene oxide of the formula IV to givecompounds of the formula I. The excess of alkylene oxide required ascompared with method A for the formation of the compounds of formula IIwas s moles of IV per mole of starting compoundm i.e. s · a moles.

The 2-carboxyethyl-methyl-phosphinic acid used in Example 60 wasprepared from the corresponding phospholane in situ by adding anadequate amount of water. The same was true for the2-carboxy-ethyl-phenyl-phosphinic acid of Example 61.

    ______________________________________                                        Example                                                                              Starting compound of formula                                                                              II                                         No.    II                   n      g (mole)                                   ______________________________________                                        1      CH.sub.3 OH          1      16.0                                                                           0.5                                       2      CH.sub.2CHCH.sub.2 OH                                                                              1      29.0                                                                          0.5                                        3      CH.sub.3 OCOCH.sub.2 OH                                                                            1      45.0                                                                          0.5                                        4      CH.sub.3CHOHCH.sub.3 1      15.0                                                                          0.25                                               ##STR17##           1      65.0 0.25                                  6      final product of Example 4                                                                         1      121.5                                                                          0.25                                      7      n-C.sub.12 H.sub.25 OH                                                                             1      37.3                                                                          0.2                                        8      HOCH.sub.2CH.sub.2 OH                                                                              2      232.8                                                                         3.6                                        9      HOCH.sub.2CHOH CH.sub.2 OH                                                                         3      184.2                                                                         2.0                                        10     HOCH.sub.2CHOHCH.sub.2 OH                                                                          3      9.2                                                                           0.1                                        11     C.sub.2 H.sub.5C(CH.sub.2 OH).sub.3                                                                3      134                                                                           1.0                                        12     C.sub.2 H.sub.5C(CH.sub.2 OH).sub.3                                                                3      11.2                                                                          0.083                                      13     pentaerythritol      4      13.6                                                                          0.1                                        14     pentaerythritol      4      3.5                                                                           0.025                                      15     sorbitol             6      12.2                                                                          0.067                                      16     α-naphthol     1      36.0                                                                          0.25                                       17                                                                                    ##STR18##           2      25.8 0.125                                 ______________________________________                                    

                  TABLE A                                                         ______________________________________                                                   molar          reaction                                                 III g   IV g    ratio            temp. time                              Ex.  (mole)  (mole)  II:III:IV                                                                            catalyst  (° C)                                                                        (h)                               ______________________________________                                        1    167.4   55      1:2.5:2.5                                                                            --        125   13                                     1.25    1.25                                                             2    134.1   44.4    1:2:2.02                                                                             1 g of sodium                                                                           125   16                                     1.0     1.01           carbonate                                         3    134.1   44.4    1:2:2.02                                                                             --        130   24                                     1.0     1.01                                                             4    134.1   44.0    1:4:4.0                                                                              --        112   13                                     1.0     1.00                                                             5    134.1   44.0    1:2:2.0                                                                              --        125   35                                     1.0     1.00                                                             6    67.0    22.5    1:2:2.04                                                                             --        130   22                                     0.5     0.51                                                             7    67.0    22.7    1:2.5:2.58                                                                           --        127   30                                     0.5     0.52                                                             8    1931    670.7   1:4:4.24                                                                             0.6g of sodium                                                                          125   20                                     14.4    15.26          carbonate                                         9    1608.9  568     1:6:6.45                                                                             --        130   24                                     12.0    12.9                                                             10   201.1   66      1:15:15.0                                                                            --        135   21                                     1.5     1.5                                                              11   804.5   278     1:6:6.32                                                                             --        140   13                                     6.0     6.32                                                             12   134.1   44      1:12:12.0                                                                            --        130   16                                     1.0     1.0                                                              13   268.2   93.4    1:20:21.2                                                                            --        122   23                                     2.0     2.12                                                             14   268.2   92.3    1:80:83.9                                                                            --        133   38                                     2.0     2.098                                                            15   268.7   93.8    1:30:31.9                                                                            --        130   23                                     2.0     2.13                                                             16   134.1   51.9    1:4:4.7                                                                              --        125   35                                     1.0     1.18                                                             17   134.1   49.4    1:8:8.98                                                                             --        130   33                                     1.0     1.12                                                             ______________________________________                                    

                  TABLE A                                                         ______________________________________                                        Example acid number n.sub.D    consistency at                                 No.     found       ° C room temperature                               ______________________________________                                        1       0.5         1.4932     oil                                                                21                                                        2       0           1.4918     oil                                                                21                                                        3       5.7         1.4860     oil                                                                21                                                        4       1.5         1.4918     oil                                                                20                                                        5       5.0         1.4780     oil                                                                20                                                        6       6.0         1.4888     oil                                                                20                                                        7       4.5         1.4773     viscous oil                                                        20                                                        8       0           1.4966     viscous oil                                                        21                                                        9       3.2         too viscous                                                                              solid                                          10      4.8         too viscous                                                                              solid                                          11      1.4         too viscous                                                                              solid                                          12      7.0         too viscous                                                                              solid                                          13      6.1         1.4982     solid                                                              20                                                        14      5.5         1.4985     solid                                                              20                                                        15      1.8         1.5081     solid                                                              20                                                        16      4.4         1.5258     solid                                                              20                                                        17      4.2         1.5181     solid                                                              20                                                        ______________________________________                                    

                  TABLE A                                                         ______________________________________                                        Example                             II                                        No.    Starting compound of formula II                                                                      n     g (mole)                                  ______________________________________                                        18     HOC.sub.2 H.sub.4SC.sub.2 H.sub.4 OH                                                                 2     18.4                                                                           0.167                                    19     N(CH.sub.2CH.sub.2OH).sub.3                                                                          3     24.9                                                                           0.25                                     20     polyethylene-glycol 600 (= average                                                                   2     150.0                                            molar weight)                 0.25                                     21                                                                                    ##STR19##             2     40.1 0.167                                22                                                                                    ##STR20##             1     47.1 0.5                                  23                                                                                    ##STR21##             1     54 0.5                                    24                                                                                    ##STR22##             1     21.6 0.2                                  25     OP(CH.sub.2 OH).sub.3  3     15.64                                                                          0.111                                    26     ClC.sub.2 H.sub.4OH    1     40.3                                                                           0.5                                      27                                                                                    ##STR23##             1     110.3 0.333                               28                                                                                    ##STR24##             2     68.0 0.125                                29     HOCH.sub.2CHBrCHBrCH.sub.2 OH                                                                        1     62                                                                             0.25                                     30     C.sub.6 F.sub.13C.sub.2 H.sub.4OH                                                                    1     36.4                                                                           0.1                                      31                                                                                    ##STR25##             1     61.1 0.125                                32                                                                                    ##STR26##             2     45.8 0.125                                ______________________________________                                    

                  TABLE A                                                         ______________________________________                                                   molar          reaction                                            Ex.  III g   IV g    ratio            temp. time                              No.  (mole)  (mole)  II:III:IV                                                                            catalyst  (° C)                                                                        (h)                               ______________________________________                                        18   134.1   52.5     1:6:7.16                                                                            --         120  39                                     1.0     1.19                                                             19   134.1   55       1:4:5.0                                                                             --         120  12                                     1.0     1.25                                                             20   268.2   90       1:8:8.16                                                                            --         125  17                                     2.0     2.04                                                             21   134.1   52.5     1:6:7.15                                                                            0.5 g of sodium                                                                          135  11                                     1.0     1.194          carbonate                                         22   201.2   89       1:3:4.04                                                                            2 g of sodium                                                                            120  11                                     1.5     2.02           carbonate                                         23   134.1   49       1:2:2.28                                                                            --         120  14                                     1.0     1.14                                                             24   134.1   46.3     1:5:5.26                                                                            --         125  27                                     1.0     1.053                                                            25   134.1   44.3     1:9:9.05                                                                            --         125  23                                     1.0     1.006                                                            26   134.1   44.6     1:2:2.08                                                                            --         130  16                                     1.0     1.04                                                             27   134.1   61       1:3:4.11                                                                            1 g of sodium                                                                            120   8                                     1.0     1.37           carbonate                                         28   134.1   46       1:8:8.36                                                                            --         135  29                                     1.0     1.045                                                            29   134.1   47.5     1:4:4.32                                                                            --         120  28                                     1.0     1.08                                                             30   84.4    29.2     1:6:6.63                                                                            (50 g of dioxan)                                                                         102  27                                     0.6     0.66                                                             31   134.1   52.8     1:8:9.6                                                                             --         130  23                                     1.0     1.20                                                             32   134.1   50.1     1:8:9.11                                                                            --         128  39                                     1.0     1.14                                                             ______________________________________                                    

                  TABLE A                                                         ______________________________________                                        Example acid number n.sub.D    consistency at                                 No.     found       ° C room temperature                               ______________________________________                                        18      8.0         1.5118     very viscous                                                       20                                                        19      6.2         1.4878     oil                                                                20                                                        20      2.6         1.4896     oil                                                                20                                                        21      1.5         1.5039     very viscous                                   22      0           1.5112     oil                                                                21                                                        23      1.3         --         liquid                                         24      2.9         1.5032     oil                                                                20                                                        25      12.0        1.5005     solid                                                              20                                                        26      0.8         1.4934     oil                                                                20                                                        27      1.5         too viscous                                                                              solid                                          28      12.4        too viscous                                                                              solid                                          29      5.2         1.4985     oil                                                                25                                                        30      1.7         too viscous                                                                              solid                                          31      10.0        too viscous                                                                              solid                                          32      13.0        1.5626     solid, viscous                                                     20                                                        ______________________________________                                    

                                      TABLE A                                     __________________________________________________________________________                                      II                                          Example                                                                            Starting compound of the formula II                                                                    n   g (mole)                                    __________________________________________________________________________    33                                                                                  ##STR27##               2   63.2 0.1                                    34.sup.+)                                                                          HOCH.sub.2CHOHCH.sub.2 OH                                                                              3   7.36                                                                          0.08                                        35.sup.+)                                                                          CH.sub.2 BrCHBrCH.sub.2 OH                                                                             1   54.5                                                                           0.25                                       36.sup.x)                                                                          HOCH.sub.2CH.sub.2OH     2   15.5                                                                           0.25                                       37.sup.x)                                                                          HOCH.sub.2CH.sub.2OH     2   31                                                                             0.5                                        38.sup.x)                                                                          HOCH.sub.2CH.sub.2OH     2   62                                                                             1.0                                        39.sup.x)                                                                          HOCH.sub.2CHOHCH.sub.2 OH                                                                              3   30.7                                                                           0.333                                      40.sup.x)                                                                          HO(C.sub.2 H.sub.4O).sub.n H average: n=13                                                             2   150                                              mole=600                      0.25                                       41   H.sub.2 NC.sub.2 H.sub.4NH.sub.2                                                                       2   25                                                                             0.42                                       42   HN[CH(CH.sub.3).sub.2 ].sub.2                                                                          1   25.3                                                                           0.25                                       43                                                                                  ##STR28##               1   23.3 0.25                                   44                                                                                  ##STR29##               1   98.6 0.5                                    45                                                                                  ##STR30##               1   82.5 0.25                                   46                                                                                  ##STR31##               2   27 0.167                                    47                                                                                  ##STR32##               2   27 0.147                                    __________________________________________________________________________

                                      TABLE A                                     __________________________________________________________________________                                  reaction                                        Example                                                                            III  IV   molar ratio    temp.                                                                             time                                        No.  g (mole)                                                                           g (mole)                                                                           II:III:IV                                                                            catalyst                                                                              (° C)                                                                      (H)                                         __________________________________________________________________________    33   134.1                                                                              45.3 1:10:10.3                                                                            --      130 11                                               1.0  1.03                                                                34.sup.+)                                                                          71   25   1:6:7.13                                                                             0.5 g of sodium                                                                       130  8                                               0.48 0.57        carbonate                                               35.sup.+)                                                                          74   30   1:2:2.72                                                                             --      130 20                                               0.5  0.68                                                                36.sup.×)                                                                    134.1                                                                              67   1:4:4.6                                                                              0.5 g of sodium                                                                       145 22                                               1.0  1.15        carbonate                                               37.sup.×)                                                                    134.1                                                                              101.6                                                                              1:2:2.2                                                                              --      135 14                                               1.0  1.1                                                                 38.sup.×)                                                                    536.4                                                                              406.4                                                                              1:4:4.4                                                                              2 g of sodium                                                                         130  8                                               4.0  4.4         carbonate                                               39.sup.×)                                                                    268.2                                                                              231  1:6:7.5                                                                              --      125 10                                               2.0  2.5                                                                 40.sup.×)                                                                    134.1                                                                              101.8                                                                              1:4:4.4                                                                              --      138  9                                               1.0  1.1                                                                 41   402  159  1:7.14:8.6                                                                           --      130 35                                               3    3.62                                                                42   134.1                                                                              44.6 1:4:4.056                                                                            --      120 32                                               1.0  1.01                                                                43   134.1                                                                              47.6 1:4:4.32                                                                             --      125 28                                               1    1.08                                                                44   201.2                                                                              66.1 1:3:3.02                                                                             --      128 17                                               1.5  1.51                                                                45   134.1                                                                              55.5 1:4:5.04                                                                             --      125 24                                               1.0  1.26                                                                46   134.1                                                                              45.9 1:6:6.25                                                                             --      130 17                                               1.0  1.043                                                               47   134.1                                                                              51.9 1:7.7:8.02                                                                           --      140 28                                               1.0  1.18                                                                __________________________________________________________________________

                  TABLE A                                                         ______________________________________                                        Example                                                                              acid number                                                                              n.sub.D      consistency                                    No.    found      ° C   at room temperature                            ______________________________________                                        33     0.8        1.5188       solid                                                            20                                                          34.sup.+)                                                                            0          too viscous  solid                                          35.sup.+)                                                                            2.7        1.4955       oil, very viscous                                                25                                                          36.sup.×)                                                                      0          --           very viscous oil                               37.sup.×)                                                                      3.1        too viscous  solid, viscous                                 38.sup.×)                                                                      4.0        too viscous  solid, viscous                                 39.sup.×)                                                                      22         very viscous solid, viscous                                 40.sup.×)                                                                      10.0       1.4942       viscous oil                                                      20                                                          41     10         1.4972       oil, very viscous                                                25                                                          42     14.3       1.4953       oil, very viscous                                                20                                                          43     2.5        1.5247       oil, very viscous                                                20                                                          44     10.3       too viscous  very viscous                                   45     3.7        too viscous  solid                                          46     7.5        too viscous  solid                                          47     1.4        too viscous  solid                                          ______________________________________                                    

                  TABLE A                                                         ______________________________________                                                  Starting compound of     II                                         Example No.                                                                             formula II        n      g (mole)                                   ______________________________________                                        48        H.sub.2 NC.sub.2 H.sub.4OH                                                                      2      15.3                                                                          0.25                                       49        C.sub.12 H.sub.24SH                                                                             1      67.3                                                                          0.33                                       50                                                                                       ##STR33##        1      18.4  0.167                                ______________________________________                                    

                  TABLE B                                                         ______________________________________                                                                            II                                        Example No.                                                                            Starting compound of formula II                                                                    n     g (mole)                                  ______________________________________                                        51                                                                                      ##STR34##           2 (2) 93 0.5                                    52                                                                                      ##STR35##           3 (3) 20.8 0.1                                  53                                                                                      ##STR36##           2 (2) 14.05 0.06                                54                                                                                      ##STR37##           2 (2) 20 0.1                                    55                                                                                      ##STR38##           3 (2) 28.5 0.15                                 56                                                                                      ##STR39##           2  (2)                                                                              48 0.5                                    57                                                                                      ##STR40##           2 (2) 54 0.5                                    58                                                                                      ##STR41##           2 (2) 32.4 0.167                                ______________________________________                                    

                  TABLE A                                                         ______________________________________                                        III      IV                       reaction                                    Ex.  g       g       molar ratio      temp. time                              No.  (mole)  (mole)  II:III:IV                                                                             catalyst (° C)                                                                        (h)                               ______________________________________                                        48   134.1   49.6    1:4:4.52                                                                              --       125   16                                     1.0     1.13                                                             49   134.1   64.7    1:3:4.41                                                                              1 g of sodium                                                                          115    9                                     1.0     1.47            carbonate                                        50   134.1   52.5    1:6:7.14                                                                              --       120   39                                     1.0     1.19                                                             ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        III      IV                       reaction                                    Ex.  g       g       molar ratio      temp. time                              No.  (mole)  (mole)  II:III:IV                                                                             catalyst (° C)                                                                        (H)                               ______________________________________                                        51   268.2   139     1:4:6.32                                                                              --       125   19                                     2.0     3.16                                                             52   120.6   52.6    1:9:12.0                                                                              --       135   26                                     0.9     1.2                                                              53   48.2    21.1    1:6:8.0 --       125   10                                     0.36    0.48                                                             54   134.1   65      1:10:14.8                                                                             --       115   20                                     1.0     1.48                                                             55   120.8   68.9    1:6:10.4                                                                              --       130   30                                     0.9     1.56                                                             56   268.2   142.3   1:4:6.46                                                                              --       125   13                                     2.0     3.23                                                             57   268.2   145     1:4:6.6 --       120   28                                     2.0     3.3                                                              58   134.1   61.5    1:6:8.4 --       120   36                                     1.0     1.4                                                              ______________________________________                                    

                  TABLE A                                                         ______________________________________                                        Example  acid number  n.sub.D   consistency at                                No.      found        ° C                                                                              room temperature                              ______________________________________                                        48       0            1.5035    oil, very viscous                                                    20                                                     49       1.5          1.4899    oil, very viscous                                                    20                                                     50       6.5          1.5118    oil, very viscous                                                    29                                                     ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        Example  acid number  n.sub.D   consistency at                                No.      found        ° C                                                                              room temperature                              ______________________________________                                        51       6.0          --        solid                                         52       5.9          --        solid                                         53       0            --        solid                                         54       0            --        solid                                         55       10.3         1.4794    viscous oil                                                         21                                                      56       9.5          --        oil                                           57       9.5          --        oil                                           58       3.0          1.4921    oil                                                                 20                                                      ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        Example                     n      V                                          No.     Starting compound V (s)    g (mole)                                   ______________________________________                                        59                                                                                     ##STR42##          1 (1)  18.5 0.1                                   60                                                                                     ##STR43##          2 (2)  15.2 0.1                                    61.sup.+)                                                                             ##STR44##          2 (2)  13.06 0.061                                62                                                                                     ##STR45##          2 (1)  105.1 0.1                                  ______________________________________                                    

                  TABLE B                                                         ______________________________________                                                                reaction                                              Example                                                                              III      IV       molar ratio                                                                           cata-                                                                              temp.                                                                              time                               No.    g (mole) g (mole) V:III-IV                                                                              lyst (° C)                                                                       (h)                                ______________________________________                                        59     134.1    53.2     1:10:12.1                                                                             --   125   23                                       1.0      1.29                                                          60     120.8    48.9     1:9:11.1                                                                              --   145   13                                       0.9      1.11                                                          61.sup.+)                                                                            48       16.2     1:4:6.1 --   130   24                                       0.245    0.37                                                          62     107.2    68.7     1:4:7.8 --   135   12                                       0.8      1.56                                                          ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        Example                                                                             acid number                                                                              n.sub.D                                                      No.   found      ° C                                                                            consistency at room temperature                      ______________________________________                                        59    8.9        1.5027  viscous oil                                                           20                                                           60    8.4        --      solid                                                61.sup.+)                                                                           2.3        --      solid                                                62    0.9        --      solid                                                ______________________________________                                    

EXAMPLE 63: (stepwise reaction)

(a₁.1) In a four-neck flask provided with stirrer, thermometer, refluxcondenser and gas inlet tube,

134.1 g (1 mole) of 2-methyl-2,5-dioxo-1-oxa-phospholane-2 were heatedto 110° C, while extremely pure nitrogen was passed over the same.Within 25 minutes,

104.2 g (1 mole) of methyl-diglycol (CH₃ --O--C₂ H₄ O--C₂ H₄ --OH) wereadded dropwise under air cooling. The reaction temperature wasmaintained between 110° and 118° C.

After the phospholane peak at 5.5 μ had disappeared, the mixture wascooled. The output weight was 238.3 g, the acid number 248.8(calculated: 235.0), the refractive index n_(D) ²⁰ = 1.4706, theP-content 13.0% (calculated: 13.0%).

(a₂.1) At a temperature of from 128 to 132° C,

45.7 g (1.037 moles) of alkylene oxide were introduced in the gaseousstate within 24 hours, while stirring vigorously, without pressure, into

238 g (1 mole) of the "acid (1)" obtained according to (a₁.1) of theformula ##STR46## in the same rate in which it was consumed. In thecourse of this process, the acid number was reduced to 2.8. After theintroduction had been completed, volatile compounds were drawn offduring 30 minutes at 110° C, under a pressure of 30 Torr. The outputweight was then 284 g, the refractive index n_(D) ²⁰ was 1.4724, theP-content 10.9% (calculated: 10.9%).

(a₁.2) According to (a₁.1) at a temperature of about 125° C,

67 g (0.5 mole) of the phospholane were added within 5 minutes to

142 g (0.5 mole) of the "ester (1)" obtained according to (a₂.1) of theformula ##STR47## The output weight was 201 g, the acid number 145.6(calculated: 134.0), the refractive index n_(D) ²⁰ was 1.4875, theP-content 14.8% (calculated: 14.8%).

(a₂.2) According to process (a₂.1) at a reaction temperature in therange of from 128° to 132° C,

22 g (0.5 mole) of ethylene oxide were introduced within 26 hours into

200 g (0.5 mole) of the "acid (2)" thus obtained of the formula##STR48## and upon completion of the reaction, easily volatile compoundswere drawn off. The output weight was

231 g, the acid number was 2.7, the refractive index n_(D) ²⁰ was1.4831, and the P-content 13.4% (calculated: 13.4%).

(a₁.3) At 120° C,

115.5 g (0.25 mole) of the "ester (2)" thus obtained of the formula##STR49## were reacted with

33.5 g (0.25 mole) of the phospholane according to process (a₁.1). Theoutput weight was 149 g, the acid number 96.8 (calculated: 94.0), therefractive index n_(D) ²⁰ was 1.4922 and the P-content 15.6%(calculated: 15.6).

(a₂.3) At a temperature of 130° C,

11.0 g (0.25 mole) of ethylene oxide were introduced, according toprocess (a₂.2) into

149 g of the "acid (3)" thus obtained which had the formula ##STR50##

160 Grams of the "ester (3)" of the formula ##STR51## were obtained. Theacid number of the product was 5.8, the refractive index n_(D) ²⁰ was1.4839, and the P-content 14.5% (calculated: 14.5%).

The compounds thus obtained were at room temperature oils showing aslightly yellow color shade.

EXAMPLE 64

1287 Grams (9.6 moles) of 2-methyl-2,5-dioxo-1-oxa-phospholane-2 wereintroduced into a V4A autoclave having a capacity of 3 liters and wereheated, while nitrogen was passed over, to a temperature of 120° C.Subsequently,

149 grams (2.4 moles) of glycol and

0.6 gram of sodium carbonate were added as catalysts within 40 minutes.At a temperature of from 135° to 140° C,

423 grams (9.61 moles) of liquid ethylene oxide were pressed in withnitrogen as auxiliary gas, while stirring rapidly, within 3 hours and ata pressure being formed which was in the range of from 2.8 to 3atmospheres. The mixture was continued to be stirred for another hour,was cooled to 110° C, the tension was released to normal pressure, andthe contents of the autoclave were evacuated.

As a result, 1869 g of an oil showing a slightly yellow color shade wereobtained, which oil had the acid number of 1.8. A P-content of 15.9% wasdetermined (calculated: 16.0%); n_(D) ²² = 1.4969.

C. General preparation method for Examples 65 through 76

(Table C)

At room temperature, a moles (column 4) of the basis compounds offormula II were added to at least a × n × m moles (column 6) of the1,2-alkylene carbonates of the formula V, and another a × n × m moles(column 5) of 2,4-dioxo-2-methyl-1-oxaphospholane, in short termed"phospholane" were added. After the addition of b grams of an alkalimetal catalyst (column 8) the mixture was heated and was maintained forc hours (column 10) at the reaction temperature d (column 9). In thecourse of this process, at least a × n × m moles of carbon dioxideescaped, according to the amount of 1,2-alkylene carbonate V (column 6)added, which could be detected for example quantitatively by means of agas meter and/or qualitatively by way of a simple bubble counter. Afterthe termination of the carbon dioxide development the reaction mixturewas cooled, and the output weight as well as the acid number and -- ifpossible -- the refractive index ( n_(D)) were determined. As to theirIR and NMR spectrums and their other physical and chemical propertiesand those with respect to application in technology the reactionproducts corresponded to those compounds that had been prepared withalkylene oxides. In Examples 65 through 75, the 1,2-alkylene carbonate Vwas identical with ethylene carbonate, in Example 76 with 1,2-propylenecarbonate.

General preparation method for Examples 65 through 76

(Table D)

In order to prepare the basis compounds of formula II in situ, the sameprocess was applied as in method C with the difference that instead ofthe compounds of formula II, use was made of a moles of phenols,phosphonic, phosphinic or carboxylic acids as starting compounds with sphenolic or acid terminal groups and n' terminal groups of the type (XH)of the invention in the molecule. In the first reaction step, a moles ofcompounds of the formula II with n × n' + s (column 3) were formed inthe mixture of these compounds with the respective phospholane III and1,2-alkylene carbonate V, by the addition of one 1,2-alkylene carbonateeach to a phenolic or acid terminal group, which products continued toreact, as has been described under A, with the phospholane of theformula III and a further amount of 1,2-alkylene carbonate of theformula V to give compounds of formula I with primary alcohol groups.The excess amount of 1,2-alkylene carbonate V required in contrast tomethod C for the formation of the said compound of the formula II was amoles per mole of starting compound, i.e. s · a moles.

The 2-carboxyethyl-methyl-phosphinic acid used in Example 81 wasproduced in the form of its di-sodium salt from the correspondingphospholane in situ by the addition of an adequate amount of sodiumcarbonate.

The phosphonic acid-semi-ester of Example 82 was used from the start inthe form of the sodium salt.

    TABLE A      III g  cata- reaction acid  consistency Ex- Starting compound of  II g     (axnxm V g molar ratio lyst temp. time number n.sub.D at room tem- ample     the formula II n (a moles) moles (mole) II:II:IV (g) (° C) (h)     found °      C perature                                                  65 HOCH.sub.     2CH.sub.2OH 2 149.0 1287.1 866.6 1:4:4.2 sodium 190 0 3.4 1.4987 oil        carbonate    2.4 9.6 9.84  2.4    20 66 HOCH.sub.2CHOHCH.sub.2 OH 3     3.8 134.1 96.8 1:24:26.4 sodium 185 4 1.2 too vis- solid,     carbonate    cous viscous    0.042 1.0 1.1  1.0 67 pentaerythritol 4 8.5     134.1 92.5 1:16:16.8 sodium 190 4 0.7 too vis- solid,        1 carbonate        cous viscous    0.0625 1.0 1.05  1.0 68 pentaerthritol 4 17.0 134.1     92.5 1:8:8.4 sodium 190 3 0.5 too vis- solid,        carbonate    cous     viscous    0.125 1.0 1.0  1.0 69 sorbitol 6 15.2 134.1 96.8 1:12:13.2     sodium 185 6 10.5 too vis- solid,        carbonate    cous viscous     0.83 1.0 1.1  1.0 70 C.sub.18H.sub.37OH 1 54 134.1 96.8 1:5:5.5 sodium     185 9 0.5 too vis- solid,        carbonate    cous viscous    0.2 1.0     1.1  0.2 71 HOC.sub.2 H.sub.4NC.sub.2 H.sub.4OH 2 12.2 134.1 96.8     1:10:11 dimethyl- 190 9 0.4 too vis- solid,        lauryl-    cous     viscous        amine    0.1 1.0 1.1  1 72 H.sub.2 NC.sub.2      H.sub.4NHC.sub.2 H.sub.4NH.sub.2 3 17.2 134.1 96.8 1:6:6.6 -- 180 9 10     too vis- solid,    0.17 1.0 1.1      cous viscous 73      ##STR52##      2 26.3 134.1 96.8 1:8:8.8 sodium carbonate 195 5 0.5 too vis-cous     solid, viscous    0.1251.0 1.1  1 74 oleylamine 1 26.7 67.0 48.4 1:5:5.5     -- 190 9 4.1 too vis- solid,            cous viscous    0.1 0.5 0.55        dimethyl- 75 C.sub.23 H.sub.25SH 1 10.1 67.0 52.8 1:10:12 lauryl- 180     3 0.5 too vis- solid, viscous    0.05 0.5 0.6  amine    cous        0.5     76 HOC.sub.6 H.sub.12OH 2 29.5 134.1 121.5 1:4:48 sodium 195 12 9.8     1.4842 liquid, oily    0.25 1.0 1.2  carbonate    21 solid, viscous       3

    TABLE D      III g  cata- reaction acid  consistency Ex- Starting compound of n II g (     axnxm V g molar ratio lyst temp. time number n.sub.D at room tem- ample     the formula II (s) (a moles) moles (mole) II:II:IV (g) (° C) (h)     found °      C perature      77      ##STR53##      22 108.80.2 168.22.0 224.02.55 1:10:12.75 sodiumcarbonate1 g 185 5 0.5     too vis-cous viscous 78 C.sub.11 H.sub.23COOH 1 40.1 107.3 96.8 1:4:5.5     sodium 170 8 0.3 too vis- solid, viscous   1 0.2 0.8 1.1  carbonate     cous        0.5 79      ##STR54##      22 19.40.1 107.30.8 96.81.1 1:8:11 sodiumcarbonate0.5190 9 1.2 too     vis-cous solid, viscous 80      ##STR55##      22 18.60.1 134.11.0 114.41.1 1:10:13 potassiumcarbonate1.0 185 6 8.6     too vis-cous solid, viscous 81      ##STR56##      22 3.80.025 134.11.0 92.41.05 1:4:42 contained inII 190 4 2 too     vis-cous solid, viscous 82      ##STR57##      11 17.40.113411 96.81.05 1:10:11 contained inII 180 5 4.3 1.494140     highly viscous

EXAMPLE 83: (Step-by-step process)

31 g (0.5 mole) of ethylene glycol,

88.1 g (1.0 mole) of ethylene carbonate,

134.1 g (1.0 mole) of 2,5-dioxo-2-methyl-1,2-oxophospholane("phospholane") and

1.0 g of sodium carbonate (as catalyst) were heated to 185° C, whilestirring, and were maintained for 8 hours at this temperature. In thecourse of this process, 44 g (1.0 mole) of carbon dioxide escaped. Theacid number was 12.3. The refractive index n_(D) ²⁰ was 1.4928. Afterthe addition of further

105.6 g (1.2 moles) of ethylene carbonate and

134.1 g (1.0 mole) of "phospholane", the mixture was again heated for 6hours at 190° C, with further 52.7 g (1.2 moles) of carbon dioxideescaping in the process. After cooling,

396 g of reaction product were left, which had an acid number of 4.6 anda refractive index n_(D) ²⁰ of 1.4989.

EXAMPLES OF APPLICATION EXAMPLE I

A coarse-threaded needle felt floor covering consisting of a polyesterfiber core and a polyamide upper surface in the ratio of 65 : 35 wastreated on a two-roll padding mangle with an aqueous solution having thefollowing composition:

350 g/l of a reaction product of 1 mole of glycol, 4 moles ofphospholane and 4.3 moles of ethylene oxide analogous to Example 8,furthermore, 160 g/l of trimethylol-melamine-trimethylether, 3.5 g/l ofzinc chloride, 200 g/l of a 40% plastic dispersion of ethylacrylate/acrylonitrile/N-methylolacrylamide copolymer in the ratio of6:3:1.

The squeezing-off effect was 100%. Subsequently the material was driedfor 25 minutes at 140° C.

The needle felt showed a very good retention of shape and elasticity andalso had a very good capacity of being reeled off.

The needle felt showed a very good flameproof effect which lasted forseveral shampooings and fine washings up to 50° C.

The flameproofing test was effected according to DIN (German IndustrialStandard) 54 333, with a determination of the flame spreading rate oftextile materials, or according to US Motor Vehicle Safety Standard No.302 (US-MVSS 302).

When the test sample was only finished with 200 g/l of the plasticdispersion mentioned in the Example, it continued to burn in full widthafter removal of the flame source. The flame front covered a measuringdistance of 10 cm within a time of 3 minutes and 35 seconds. Incontradistinction thereto, the needle felt material finished accordingto the invention did not continue to burn after removal of the testflame. Only an after-burn effect could be found outside the measuringdistance, which lasted for 3 to 8 seconds. After two fine washings with2 g/l of a commercial high-duty detergent (washing time 15 minutes eachtime at 40° C), the needle felt did not continue to burn eitherfollowing the removal of the flame source. The after-burn period hadonly been increased to 25 to 50 seconds. Also after the fifthshampooing, the needle felt did not continue to burn either. Theafter-burn effect again lasted for only 45 seconds.

EXAMPLE II

The needle felt described in Example I was treated according to the sameapplication process with the aqueous impregnation bath indicated below:

400 g/l of a reaction product of 1 mole of glycerol, 6 moles ofphospholane and 6.45 moles of ethylene oxide (analogous to Example 9),160 g/l of trimethylol-melamine-trimethylether, 4 g/l of zinc chloride,200 g/l of a 40% plastic dispersion of ethyleneacrylate/acrylonitrile/N-methylolacrylamide (6:3:1) copolymer.

The squeezing-off effect was 95%. Subsequently the material was driedfor 25 minutes at 145° C in a drying cabinet with circulating air andwas hardened at the same time.

The needle felt showed a very good permanent flameproof effect whichlasted for several wet treatments (shampooings or fine washings at 40°C).

The feel was elastic, and the needle felt showed a good retention ofshape, which was still excellent after several wet treatments.

Instead of 160 g/l of trimethylol-melamine-trimethylether, there mayalso be used as cross-linking component of the terminal hydroxyl groupsof the phosphinic acid ester being present, 250 g/l of a 50%dimethylol-dihydroxyethylene-urea solution. The needle felt thusfinished also showed a permanent flameproof effect as well as a goodretention of shape.

EXAMPLE III

A needle felt floor covering having a weight of 700 g per square meterand consisting of a fine-threaded polypropylene core and acoarse-threaded upper surface of polypropylene fibers was treated on atwo-roll padder with the aqueous impregnation solution which had beendescribed in Example I.

The squeezing-off effect was 100%. Subsequently the material was treatedfor 30 minutes at 135° C.

The flameproof effect was excellent, it remained unaltered even afterseveral wet treatments, The feel was very flexible, and the needle feltmaintained its retention of shape also after having been subjected towet treatments. The very smooth feel of the polypropylene fiber wasimproved by the finish and became more textile.

EXAMPLE IV

Similar good effects were also obtained on the needle felt described inExample III, if the finishing was carried out according to thespecification given in Example II, i.e. with a reaction product of 1mole of glycerol, 6 moles of phospholane and 6.45 moles of ethyleneoxide and the additional and/or cross-linking components described.

The dyring and/or condensation was carried out at 135° C.

EXAMPLE V

A needle felt covering used in the automobile industry which wasdesigned for covering the trunk compartment and the passenger room andwhich consisted of 50% of fine-threaded polyamide fibers and 50% ofviscose staple fibers having a weight per square meter of 550 g, wasimpregnated with a solution containing 300 g/l of the reaction productof 1 mole of glycol, 4 moles of phospholane and 4.3 moles of ethyleneoxide (analogous to Example 8), 120 g/l ofhexamethylol-melamine-pentamethylether, 180 g/l of a 50%polyvinylacetate dispersion and 5 g/l of ammonium chloride. Thetreatment was effected on a two-roll padder with a squeezing-off effectof 95%. The material was then subjected to drying and condensation in adrying cabinet for 25 minutes at 150° C.

The needle felt showed a pronounced permanent flameproof effect. It wasflexible and could well be pasted on metal sheets.

EXAMPLE VI

A textile wall covering which consisted of 25% of polyester fibers and75% of glass fibers and which was to serve as covering fabric for aflameproof polyurethane foam was treated with an impregnation solution,as has been described in Example II, in a way that it was drawn off froman impregnation solution via a steel roller. As counter roller there wasused a rubber roller which was besides wrapped with a cotton knittedfabric (lapping). The liquor pick-up was 150%. After a drying period of10 minutes at 150° C, a textile wall covering was obtained which wasnon-slipping andd flameproof to an excellent degree.

EXAMPLE VII

An impregnation solution contained 300 g/l of a reaction product of 1mole of pentaerythritol, 20 moles of phospholane and 21.4 moles ofethylene oxide (analogous to Example 13). The phosphorus content of thereaction product was about 15.6%.

As cross-linking component, 100 g/l ofhexamethylol-melamine-pentamethylether were added as well as 5 g/l ofammonium chloride as catalyst. A fine-threaded polyester needle felthaving a weight per square meter of 350 g was treated with theimpregnation solution described on a two-roll padder. It was squeezedoff to a liquor pick-up of 100%, then dried at 145° C. The needle feltwhich had very good flameproof properties was suitable as insulatingmaterial for building protection.

EXAMPLE VIII

A needle felt floor overing consisting of 50% of polyamide and 50% ofpolyester fibers and having a weight per square meter of 650 g wastreated with the aqueous impregnation solution specified below:

400 g/l of a reaction product of 1 mole of trimethylol-propane, 12 molesof phospholane and 12 moles of ethylene oxide, 180 g/l of a 80%trimethylol-melamine-trimethylether solution, 250 g of a 50%polyvinylacetate dispersion and 20 g/l of a 40%2-amino-2-methyl-propanol-hydrochloride solution.

After the treatment on a two-roll padder with a squeezing-off effect of105% and drying period of 25 minutes at 145° C, a needle felt wasobtained which ahd a flexible feel and which showed excellent flameproofproperties.

EXAMPLE IX

The needle felt described in Example I was treated with an aqueousfinishing bath having the composition specified below, on a two-rollpadder:

350 g/l of a reaction product of 1 mole of benzoic acid, 6 moles ofphospholane and 6.6 moles of ethylene oxide,

100 g/l of hexamethylol-melamine-pentamethylether,

20 g/l of a 40% 2-amino-2-methyl-propanol-hydrochloride solution, and

200 g/l of a 40% plastic dispersion ofethylacrylate/acrylonitrile/N-methylolacrylamide (6:3:1) copolymer.

The squeezing-off effect was about 105%. Subsequently the material wasdried for 25 minutes at 140° C in a laboratory drying cabinet withcirculating air and hardened.

EXAMPLE X

A polypropylene needle felt consisting of a fine-threaded core and acoarse-threaded upper surface and having a weight per square meter of750 g was treated on a two-roll padder with an aqueous impregnationsolution which contained 320 g/l of a reaction product of 1 mole oflactic acid-methylester with 2 moles of phospholane and 2.02 moles ofethylene oxide; 120 g/l of hexamethylol-melamine-pentamethylether;

5 g/l of ammonium chloride and

200 g/l of a 40% plastic dispersion, as has been described in ExampleIX.

The squeezing-off effect was 100%. The material was dried according toExample IX, however, only at 175° C.

The needle felt thus treated had a good retention of shape, was flexibleand was marked by a very good permanent flameproof effect.

EXAMPLE XI

The needle felt described in the previous Example was treated with anaqueous impregnation solution having the following composition:

320 g/l of a reaction product of 1 mole of allyl alcohol, 2 moles ofphospholane and 2 moles of ethylene oxide,

120 g/l of hexmethylol-melamine-pentamethylether,

6 g/l of ammonium chloride,

180 g/l of a 40% plastic dispersion, as has been described in ExamplesIX and X.

The squeezing-off effect on a two-roll padder was 105%. After a dryingperiod of 28 minutes at 120° C the needle felt thus treated showed aflexible feel as well as a good retention of shape. The very goodflameproof effect lasted for several wet treatments.

The same good flameproof effects -- also with respect to permanence --were obtained, if instead of the above reaction product of 1 mole ofallyl alcohol, 2 moles of phospholane and 2 moles of ethylene oxide, usewas made of a reaction product having the following composition:

1 Mole of methanol, 2.5 moles of phospholane and 2.5 moles of ethyleneoxide. The composition of the other components remained unaltered.

EXAMPLE XII

The needle felt floor covering described in Example I was treated on atwo-roll padder with the following finishing bath:

280 g/l of a reaction product of 1 mole of ethylene-diamine, 7.14 molesof phospholane and 8.6 moles of ethylene oxide,

160 g/l of trimethylol-melamine-trimethylether

210 g/l of a 40% plastic dispersion ofethylacrylate/acryonitrile/N-methylolacrylamide in the ratio of 6:3:1,

35 g/l of a 40% 2-amino-2-methyl-propanol-hydrochloride solution.

The squeezing-off effect was 97%. The drying was carried out for 25minutes at 145° C. The needle felt was flexible and showed a goodretention of shape. The flameproof effect was very good and lasted forseveral shampooings and washings.

The same good effects were obtained, when instead of the above-describedreaction products, use was made of the following reaction products:

1. 1 Mole of m-phenylene-diamine and 6 moles of phospholane and 6.76moles of ethylene oxide.

2. 1 Mole of benzidine and 7.7 moles of phospholane and 8.02 moles ofethylene oxide.

The amounts used were 300 g/l each time.

EXAMPLE XIII

A needle felt floor covering which consisted of 50% of fine-threadedpolyester fibers with 50% of staple fibers and which was used asflameproof insulating material for building protection was treated withan aqueous impregnation solution of the following composition:

370 g/l of a reaction product of 1 mole of polyglycol 600, 8 moles ofphospholane and 8.9 moles of ethylene oxide,

160 g/l of trimethylol-melamine-trimethylether.

200 g/l of a 50% polyvinylacetate dispersion,

5 g/l of ammonium chloride.

After the treatment on a two-roll padder with a squeezing-off effect ofabout 105% the material was dried for 25 minutes at 145° C and hardened.The flameproof effect was excellent.

EXAMPLE XIV

A needle felt floor covering, such as has been described in Example I,was treated on a two-roll padder with a finishing bath having thefollowing composition:

250 g/l of a reaction product of 1 mole of1,2-ethane-bis-methylphosphinic acid, 4 moles of phospholane, 6.3 molesof ethylene oxide,

230 g/l of a 50% hexamethylol-melamine-pentamethylether solution,

200 g/l of a 40% plastic dispersion ofethylacrylate/acrylonitrile/N-methylolacrylamide copolymer in the ratioof 6:3:1,

25 g/l of a 40% 2-amino-2-methyl-propanol-hydrochloride solution.

The squeezing-off effect was about 98%. The drying and condensation werecarried out for 28 minutes at 145° C.

The needle felt thus finished did not show any hardening of the feel. Itwas filled, but flexible and had a good retention of shape. Theflameproof effect was excellent and lasted for several wet treatments(shampooings and fine washings).

EXAMPLE XV

The needle felt described in Example I was treated with the samefinishing bath which has also been mentioned in Example I. Instead ofthe 40% plastic dispersion ofethylacrylate/acrylonitrile/N-methylacrylamide 6:3:1 described, use wasmade of 160 g/l of an about 45%styrene/butylacrylate/acrylonitrile/methacrylic acid copolymerdispersion (ratio of 16:61:25:2:1).

A good permanent flameproof effect was also obtained, and the feel wasfull and flexible. The needle felt also showed a good retention ofshape.

EXAMPLE XVI

A tufted carpet material having a weight per square meter of 600 g/m²and consisting of a polyamide loop pile of a height of 6 mm, which wastufted on a carrier material of needled polypropylene fleece, wasprovided with a pre-coating of the following composition:

300 Parts of a reaction product of 1 mole of glycol, 4 moles of2,5-dioxo-2-methyl-1,2-oxa-phospholane and 4.3 moles of ethylene oxideor ethylene carbonate,

120 parts of a 80% trimethylol-melamine-trimethylether solution,

500 parts of a 3.5% methyl-hydroxyethyl-cellulose solution,

150 parts of a 50% butadiene-styrene dispersion (60:40),

75 parts of water,

5 parts of ammonium chloride,

600 parts of chalk.

The pre-coating was applied by means fo a rubber squeeze and was driedfor 10 minutes at 140° C. The dry coating amount had a weight of about800 g/m².

The tufted carpet thus treated showed a flexible feel, and theimpregnative solution had not penetrated into the pile threads. The pilestill showed its original looseness. The pile threads were excellentlyattached to the basic fabric.

Subsequently a carpet back coating was also applied with a rubbersqueeze by way of a foaming process. The coating bath consisted of

205 parts of 50% butadiene-styrene dispersion (40/60),

14 parts of a paste containing vulcanization accelerators,

300 parts of chalk,

8 parts of a foaming agent on the basis of alkyl-naphthalenesulfonicacid-sodium salt.

The foaming was carried out in a ratio of 1:3 to the original volume.Following the doctor coating, the material was then dried for 10 minutesat 150° C. A smooth foam back was obtained which had a weight of about900 g per square meter of dry coating. In a parallel test, a section ofthe above-described tufted material was provided with a pre-coatingwhich did not contain any flameproof components. The bond coating wasagain effected by means of a 50% butadiene-styrene dispersion (60:40),chalk and methyl-hydroxyethyl cellulose as thickening agent. Afterdrying, the above-described smooth foam was applied.

When the two carpet sections were tested according to DIN standard No.54 332 following a flaming period of 15, 30 and 60 seconds, the tuftedcarpet which had not been finished with the flameproofing agent burneddown all the way, whereas the carpet with a flameproof finish did notshow any further burning or after-burn effect following the removal ofthe test flame.

According to the Nordtest method No. 7 for floor coverings, thefollowing results were found: The carpet section which did not obtainany flameproof substance in the pre-coating, did not show any flameproofeffect according to the Nordtest method No. 7. After the stack of woodhad been extinguished, the carpet section continued to burn in a widefront over the measuring mark of 60 cm. The carpet section with aflameproof finish was extinguished immediately after the extinguishingof the stack of wood and showed a burning length of 28 cm, a burningwidth of 14 cm and an after-burn effect of 30 seconds. The smooth foamback which had not been provided with a flameproof finish was notaffected by the flaming. This excellent flameproof effect was stillmaintained after five shampooings or after several wet treatments.

EXAMPLE XVII

The tufted carpet described in Example XVI was coated with a pre-coatingcomposition which contained the following components:

320 Parts of a reaction product of 1 mole of glycerol, 6 moles ofethylene oxide or ethylene carbonate,

125 parts of a 80% trimethylol-melamine-trimethylether solution,

550 parts of a 3.5% methyl-hydroxyethyl-cellulose solution,

150 parts of a 50% butadiene-styrene dispersion (60:40),

50 parts of water,

5 parts of ammonium chloride,

400 parts of chalk.

The pre-coating was applied by means of a hand-operated doctor blade andwas dried for 15 minutes at 135° C. The dry coating amount had a weightof about 870 g/m².

The tufted carpet thus treated showed a flexible feel after thetreatment. The carpet pile was not adversely affected by the treatment,as the pre-coating composition did not penetrate the basic fabric.Subsequently a tufted back coating was applied by way of the foamingprocess. The coating bath consisted of:

250 Parts of a 50% butadiene-styrene dispersion (40:60),

16 parts of a paste containing vulcanization accelerators,

275 parts of chalk,

10 parts of a foaming agent on the basis of alkyl-naphthalenesulfonicacid-sodium salt.

The foaming was carried out in a ratio of 1:3. Following the coatingwith a hand-operated doctor, the material was dried for 15 minutes at145° C. The dry coating amount of the smooth foam back had a weight of870 g per square meter.

The tufted carpet thus treated did not continue to burn after the stackof wood had been extinguished, according to Nordtest method No. 7 forfloor coverings. The burning length was 32 cm and the burning width 15cm. After two minutes, there was no sign of an after-burn.

The smooth foam of the carpet back remained unaffected and did not showany damage by burning.

The flameproof effect had an excellent fastness to shampooing and lastedfor several wet treatments.

EXAMPLE XVIII

A tufted carpet having a weight per square meter of 700 g consisted of apre-needled polypropylene fleece and a polyester pile which had a bluecolor shade and a pile height of 5 mm. It was treated with a pre-coatingcomposition which contained the following products:

250 Parts of a reaction product of 1 mole of glycol, 4 moles of2,5-dioxo-2-methyl-1,2-oxa-phospholane and 4.3 moles of ethylene oxideor ethylene carbonate,

90 parts of a 80% trimethylol-melamine-trimethylether solution,

500 parts of a 3.5% methyl-hydroxy-cellulose solution,

170 parts of a 50 % butadiene-styrene dispersion (60:40),

70 parts of water,

5 parts of zinc chloride,

400 parts of zinc chloride,

400 parts of chalk.

The pre-coating was again applied by means of a hand-operated doctorblade and was dried for 12 minutes at 150° C. The weight of the drycoating was 900 g/m².

Subsequently a smooth foam was again applied onto the carpet back, ashas been described in Examples 1 and 2.

In a parallel test a pre-coating without the flameproofing components,but with the same butadiene-styrene dispersion, was applied onto thesame material, and afterwards the carpet back coating was carried out inaccordance with Examples XVI and XVII by way of the foaming process.

According to the DIN test method No. 54 332 comprising a flaming periodof 15, 30 and 60 seconds, the carpet test sample did not continue toburn after removal of the test flame. The tufted carpet sample which hadnot been provided with a flameproofing finish did continue to burn afterremoval of the test flame. The flameproof effect lasted for severalshampooings.

EXAMPLE XIX

The tufted carpet described in Example XVIII was treated with apre-coating composition which contained the following components:

300 Parts of a reaction product of 1 mole of glycol, 4 moles of2,5-dioxo-2-methyl-1,2-oxa-phospholane and 4.3 moles of ethylene oxideor ethylene carbonate,

120 parts of a 80 % trimethylolamine-trimethylether solution,

500 parts of a 3.5 % methyl-hydroxyethyl-cellulose solution,

200 parts of a 40% plastic dispersion ofethylene-acrylate/acrylonitrile/N-methylolacrylamide copolymer in aratio of 6:3:1,

75 parts of water,

20 parts of magnesium chloride,

3 parts of citric acid,

400 parts of chalk.

The pre-coating was applied by means of a rubber squeeze and waspre-heated on a stenter frame (10 sections) at 110° C; then it washardened via a cylinder dryer for 5 minutes at 135° C. The wet coatingon the rubber squeeze had a weight of 1300 g/m² and the dry coating hada weight of about 790 g/m².

Subsequently, a butadiene-styrene back coating was applied by way of thefoaming process, as has been described in Example 1. According to theNordtest method No. 7 for floor coverings, a burning length of 32 cm anda burning width of 16 cm were found; the flameproof effect was indeedexcellent, since besides there was only an after-burn of 30 seconds.

The carpet section which did not contain any flameproof substance in thepre-coating and whose bond coating of the pile was effected only by wayof the 40% plastic dispersion ofethylacrylate/acrylonitrile/N-methylolacrylamide with the addition ofthe thickening agent methyl-hydroxy-ethyl cellulose and chalk, burned inthe flameproofing test according to the Nordtest method No. 7 beyond the60 cm mark. In this process the carpet back coating was completelydestroyed.

The flameproof finish lasted for eight shampooings and five wettreatments. Since the flameproof effect was still present to its fullextent, the cleaning processes were discontinued.

EXAMPLE XX

A tufted carpet having a weight of 750 g/m² consisted of a pre-needledpolypropylene fleece and a pile which had a brown color shade and a pileheight of 6 mm and consisted of 80% of polyacylonitrile and 20% ofpolyamide threads.

Said tufted material was given a flameproof finish, as has beendescribed in Example XVI.

According to Nordtest method No. 7 for floor coverings, a burning lengthof 45 cm and a burning width of 18 cm was found. The floor coveringwhich had not been finished with a flameproof agent burned very rapidlybeyond the 60 cm mark.

EXAMPLE XXI

A tufted carpet, as has been described in Example XVI, was treated witha pre-coating having the following composition:

280 Parts of a reaction product of 1 mole of pentaerythritol, 8 moles of2,5-dioxo-2-methyl-1,2-oxa-phospholane and 8.4 moles of ethylene oxideor ethylene carbonate,

120 parts of a dimethylolurea-dimethylester solution of 80% strength,

500 parts of a 3.5% methyl-hydroxyethyl-cellulose solution,

170 parts of a 50% butadiene-styrene dispersion (60:40),

60 parts of water,

5 parts of ammonium chloride,

400 parts of chalk.

The pre-coating was effected according to the method described inExample XVII. Subsequently the material was dried for 20 minutes at 140°C in the drying cabinet. The dry coating had a weight of 870 g/m².

The further treatment was again carried out, as has been described inExample XVI. After a foam back of synthetic latex had been applied, apre-gelatinizing was effected, then a honeycomb back was embossed on thesynthetic latex coating by means of an embossing bowl, and the materialwas vulcanized for 10 minutes at 150° C. The tufted carpet thus treatedand finished with a flameproof agent showed a highly elastic feel andmet the requirements of Nordtest method No. 7 for floor coverings.

The burning length was 32 cm, the burning width 12 cm. After the stackof wood had been extinguished, the test sample did not continue to burn,only at two places an after-burn effect of 1 minute could be observed.

The flameproof effects were fast to shampooing.

EXAMPLE XXII

A tufted carpet, as has been described in Example XVIII, was providedwith a pre-coating consisting of

230 parts of a reaction product of 1 mole of sorbitol, 12 moles of2,5-dioxo-2-methyl-1,2-oxa-phospholane and 13.2 moles of ethylene oxideor ethylene carbonate,

95 parts of a 80% trimethylol-melamine-trimethylether solution,

450 parts of a 3.3% methyl-hydroxyethyl-cellulose solution,

180 parts of a 50% butadiene-styrene dispersion (60:40),

70 parts of water,

5 parts of zinc chloride,

410 parts of chalk.

The application and further treatment was effected, as has beendescribed in Example XVIII.

A tufted carpet was obtained which had very good flameproof properties.

EXAMPLE XXIII

A printed polyamide woven carpet having a weight per square meter of 800g and a pile height of 5 mm was provided with a carpet back coating. Asfeel-improving component, a 50% polyvinylacetate dispersion was used,and a methyl-hydroxyethyl-cellulose solution as thickening agent.

A woven carpet thus finished burned down under the action of flames,however.

Said carpet was therefore provided with a carpet back finish which hadthe following composition:

300 Parts of a reaction product of 1 mole of glycol, 4 moles of2,5-dioxo-2 -methyl-1,2-oxa-phospholane and 4.3 moles of ethylene oxideor ethylene carbonate,

120 parts of a 80% trimethylol-melamine-trimethylether solution,

500 parts of a 3.5% methyl-hydroxyethyl-cellulose solution,

200 parts of a 50% polyvinylacetate dispersion,

50 parts of water,

5 parts of ammonium chloride.

The pre-coating was applied by means of a rubber squeeze and was driedfor 10 minutes at 135° C. The dry coating had a weight of about 450g/m². The flameproof carpet back finish was flexible. According to DINNo. 54 332, the carpet showed after a flaming period of 15, 30 and 60seconds an excellent flameproof effect. After removal of the test flame,the carpet did not continue to burn.

What is claimed is:
 1. Compounds of the general formula ##STR58## inwhich X is oxygenR³ is a (C₁ -C₄)-alkyl group which may be substituted,preferably monosubstituted, by halogen, especially chlorine, acylcoalkyl group having up to 8 carbon atoms, especially cyclopentyl,cyclohexyl, an alkenyl group having up to 4 carbon atoms, especiallyvinyl and allyl, a phenyl or benzyl group optionally substituted byhalogen, preferably chlorine and/or bromine, and preferably carrying 1to 3 substituents, R⁴ is hydrogen or a (C₁ -C₄)-alkyl group, preferablymethyl, R⁵ is hydrogen or a (C₁ -C₂)-alkyl group, preferably methyl,with at least one of the radicals R⁴ and R⁵ preferably being hydrogen,R⁶ is hydrogen, methyl, chloromethyl, R⁷ is hydrogen, methyl or ethyl,preferably hydrogen, m stands for numbers in the range of from 1 to 20,preferably from 2 to 20, especially 20 to 6, n stands for numbers in therange of from 1 to 6, preferably from 2 to 6, r is 0 or 1, preferably 0,Z is a n-valent radical of the group consisting of: straight-chain orbranched hydrocarbon radicals having from 1 to 18, preferably from 1 to12, carbon atoms which may be interrupted by up to 8 --O-atoms,generally up to (q/2 - 1) -- O-atoms, if q is the number of carbon atomsin Z, and/or by up to 3 --S-atoms and/or NR² radicals with R² being (C₁-C₄)-alkyl, especially methyl, and/or may be substituted by fluorine,chlorine, bromine atoms, preferably Cl and Br, while carrying preferablysubstituents in a number of up to half the H-atoms contained in Z,especially from 1 to 4; cyclohexyl radicals which may be substituted byfrom 1 to 3, preferably one straight-chain or branched and/orunsaturated alkyl radical having from 1 to 4 carbon atoms, or by a (C₁-C₄)-alkyl radical carrying preferably up to 4 F, Cl, or Br-atoms;aromatic or araliphatic radicals which are derived from benzene, alkylbenzenes having up to 18 carbon atoms, from naphthalene, diphenyl,diphenylmethane, diphenylethane or 2,2-diphenylpropane, and which may besubstituted in the nucleus by 1 or 2 methoxy and/or ethoxy groups, andwhich may be substituted in the nucleus and/or the lateral chains by F,Cl or Br-atoms, preferably carrying up to 5 substituents, orphosphate-containing radicals of the general formula ##STR59## in whichn₁, n₂ are independently from each other 0 and 1 and R⁹ stands foralkyl, hydroxyalkyl, optionally (C₁ -C₂)-alkylated and/or -dialkylatedaminoalkyl, halogeno- (preferably choloro-)alkyl having 1 to 3 carbonatoms, alkenyl having 2 or 3 carbon atoms or phenyl optionallysubstituted by 1 or 2 halogen atoms, preferably Cl or Br, R¹⁰ , r¹¹ maybe defined as R⁹ -- if the pertinent n₁ and/or n₂ equals 0 -- with therestriction that for n₁ =n₂ =0 at least one of the radicals R¹⁰ , R¹¹ isan (C₁ -C₃ )-alkylene radical or, if the pertinent n₁ and/or n₂ equals1, is a straight-chain or branched alkylene radical having from 2 to 5carbon atoms or is the radical ##STR60## or representphosphorous-containing radicals of the general formula ##STR61## withn₁, R¹⁶, R¹¹ being defined as in Z₁ and R¹² being a straight-chain orbranched (C₁ -C₆ )-alkylene, phenylene, xylylene radical or a radical##STR62## with Y = OH, NH₂ and R¹³ = (C₁ -C₃)-alkyl, orphosphorus-containing radicals of the general formula ##STR63## in whichR⁴, R⁵, R⁶, R⁷ are defined as in formula I above and R¹⁴ is defined asR³ or represents the group --O--CHR⁶ --CHR⁷.
 2. Compounds of the formulaI as claimed in claim 1, in which Z is alkyl with 2 to 6 carbon atoms, Xis oxygen, n and m represent integers of 2 to 6, r equals 0, R⁴ to R⁷stand for hydrogen or methyl, and R³ is methyl, ethyl or phenyl. 3.Process for the preparation of compounds of formula I, which comprisesmixing a compound of the formula

    Z(--X--H).sub.n                                            II

(a₁) with the about n times molar amount of a phospholane of the formula##STR64## heating it at a temperature of from 0° to 180° C, preferably80° to 150° C, to give a phosphinic acid of the formula ##STR65## and,when this reaction has been completed, which can be seen from thedisappearing of the phospholane peak at 5 500 mμ, (a₂)mixing the productthus obtained with the about n times molar amount of an alkylene oxideof the formula ##STR66## reacting it at a temperature of from 80° to180° C, preferably from 100° to 150° C, to give a phosphinicacid(hydroxyalkyl)-ester of the formula ##STR67## and, when thisreaction has been completed, which can be seen from the acid numberbeing 0 at the above reaction temperatures, i.e. from 80° to 180° C,preferably from 100° to 150° C, repeating the operation a₁ (m-1 + r)times and following every operation a₁, repeating the operation a₂ --(m - 1) times altogether --, or, preferably, (b₁) mixing a compound ofthe formula II with the about n(m+r) times molar amount of a phospholaneof the formula III at a temperature of from 80° to 180° C, preferablyfrom 100° to 150° C and, after the reaction heat has cooled off, (b₂)mixing the product with the about n·m times molar amount of an alkyleneoxide of the formula IV and further maintaining the mixture, preferablywhile stirring, at the reaction temperature, until the reaction has beencompleted, which can be seen from the disappearing of the phospholanepeak and/or when r equals 0, also of the acid number.
 4. Process asclaimed in claim 3, which comprises mixing the phosphinic acid of theformula IIa(a₂) with the about n times molar amount of an alkylenecarbonate of the formula ##STR68## reacting it at a temperature of from130° to 250° C, preferably from 160° to 220° C, to give a phosphinicacid(hydroxyalkyl)-ester of the formula ##STR69## and after the reactionhas been completed, which can be seen from the disappearing of the acidnumber at the above-mentioned reaction temperatures, repeating theoperation a₁ (m-1+r) times and following every operation a₁, repeatingthe operation a₂ -- (m - 1) times altogether--, or, preferably, (b₁)mixing a compound of the formula II with the n·m times molar amount of aphospholane of the formula III at a temperature of form 10° to 180° C,preferably from 20° to 120° C, and after the reaction heat has cooledoff, (b₂) mixing the product with the about n·m times molar amount of analkylene oxide of the formula IV and further maintaining the mixture,preferably while stirring, at the reaction temperature, until thereaction has been completed, which can be seen from the disappearing ofthe carbon dioxide development and/or for r = 0, also of the acidnumber.